Natural production of organohalogen compounds handbook of environmental chemistry

Editor-in-Chief
Prof. em. Dr. Otto Hutzinger
University of Bayreuth
c/o Bad Ischl Office
Grenzweg 22
5351 Aigen-Vogelhub, Austria
E-mail:

Advisory Board
Dr. T.A.T. Aboul-Kassim

Prof. Dr. D. Mackay

Department of Civil Construction
and Environmental Engineering,
College of Engineering,
Oregan State University, 202 Apperson Hall,
Corvallis, OR 97331, USA

Department of Chemical Engineering
and Applied Chemistry
University of Toronto
Toronto, Ontario, Canada M5S 1A4

Dr. D. Barcelo
Environment Chemistry
IIQAB-CSIC
Jordi Girona, 18
08034 Barcelona, Spain

Prof. Dr. P. Fabian
Chair of Bioclimatology
and Air Pollution Research
Technical University Munich
Hohenbacherstraße 22
85354 Freising-Weihenstephan, Germany

Prof. Dr. A.H. Neilson
Swedish Environmental Research Institute
P.O.Box 21060
10031 Stockholm, Sweden
E-mail:

Prof. Dr. J. Paasivirta
Department of Chemistry
University of Jyväskylä
Survontie 9
P.O.Box 35
40351 Jyväskylä, Finland

Dr. H. Fiedler

Prof. Dr. Dr. H. Parlar

Scientific Affairs Office
UNEP Chemicals
11–13, chemin des Anémones
1219 Châteleine (GE), Switzerland
E-mail:

Institute of Food Technology
and Analytical Chemistry
Technical University Munich
85350 Freising-Weihenstephan, Germany

Prof. Dr. H. Frank
Chair of Environmental Chemistry
and Ecotoxicology
University of Bayreuth
Postfach 10 12 51
95440 Bayreuth, Germany

Department of Veterinary
Physiology and Pharmacology
College of Veterinary Medicine
Texas A & M University
College Station, TX 77843-4466, USA
E-mail:

Prof. Dr. M. A. K. Khalil

Prof. P.J. Wangersky

Department of Physics
Portland State University
Science Building II, Room 410
P.O. Box 751 Portland, Oregon 97207-0751, USA
E-mail:

University of Victoria

Centre for Earth and Ocean Research
P.O.Box 1700
Victoria, BC, V8W 3P6, Canada
E-mail:

Prof. Dr. S.H. Safe


Preface

Environmental Chemistry is a relatively young science. Interest in this subject,
however, is growing very rapidly and, although no agreement has been reached
as yet about the exact content and limits of this interdisciplinary discipline, there
appears to be increasing interest in seeing environmental topics which are based
on chemistry embodied in this subject. One of the first objectives of Environmental Chemistry must be the study of the environment and of natural chemical
processes which occur in the environment. A major purpose of this series on
Environmental Chemistry, therefore, is to present a reasonably uniform view of
various aspects of the chemistry of the environment and chemical reactions
occurring in the environment.
The industrial activities of man have given a new dimension to Environmental Chemistry. We have now synthesized and described over five million
chemical compounds and chemical industry produces about hundred and fifty
million tons of synthetic chemicals annually. We ship billions of tons of oil per
year and through mining operations and other geophysical modifications, large
quantities of inorganic and organic materials are released from their natural
deposits. Cities and metropolitan areas of up to 15 million inhabitants produce
large quantities of waste in relatively small and confined areas. Much of the
chemical products and waste products of modern society are released into the
environment either during production, storage, transport, use or ultimate
disposal. These released materials participate in natural cycles and reactions
and frequently lead to interference and disturbance of natural systems.

Environmental Chemistry is concerned with reactions in the environment. It
is about distribution and equilibria between environmental compartments.
It is about reactions, pathways, thermodynamics and kinetics. An important
purpose of this Handbook, is to aid understanding of the basic distribution and
chemical reaction processes which occur in the environment.
Laws regulating toxic substances in various countries are designed to assess
and control risk of chemicals to man and his environment. Science can contribute in two areas to this assessment; firstly in the area of toxicology and
secondly in the area of chemical exposure. The available concentration
(“environmental exposure concentration”) depends on the fate of chemical
compounds in the environment and thus their distribution and reaction behaviour in the environment. One very important contribution of Environmental
Chemistry to the above mentioned toxic substances laws is to develop laboratory
test methods, or mathematical correlations and models that predict the environ-


VIII

Preface

mental fate of new chemical compounds. The third purpose of this Handbook is
to help in the basic understanding and development of such test methods and
models.
The last explicit purpose of the Handbook is to present, in concise form, the
most important properties relating to environmental chemistry and hazard
assessment for the most important series of chemical compounds.
At the moment three volumes of the Handbook are planned. Volume 1 deals
with the natural environment and the biogeochemical cycles therein, including
some background information such as energetics and ecology. Volume 2 is concerned with reactions and processes in the environment and deals with physical
factors such as transport and adsorption, and chemical, photochemical and
biochemical reactions in the environment, as well as some aspects of pharmacokinetics and metabolism within organisms.Volume 3 deals with anthropogenic
compounds, their chemical backgrounds, production methods and information

about their use, their environmental behaviour, analytical methodology and
some important aspects of their toxic effects. The material for volume 1, 2 and 3
was each more than could easily be fitted into a single volume, and for this
reason, as well as for the purpose of rapid publication of available manuscripts,
all three volumes were divided in the parts A and B. Part A of all three volumes is
now being published and the second part of each of these volumes should appear
about six months thereafter. Publisher and editor hope to keep materials of the
volumes one to three up to date and to extend coverage in the subject areas by
publishing further parts in the future. Plans also exist for volumes dealing with
different subject matter such as analysis, chemical technology and toxicology,
and readers are encouraged to offer suggestions and advice as to future editions
of “The Handbook of Environmental Chemistry”.
Most chapters in the Handbook are written to a fairly advanced level and
should be of interest to the graduate student and practising scientist. I also hope
that the subject matter treated will be of interest to people outside chemistry and
to scientists in industry as well as government and regulatory bodies. It would
be very satisfying for me to see the books used as a basis for developing graduate
courses in Environmental Chemistry.
Due to the breadth of the subject matter, it was not easy to edit this Handbook. Specialists had to be found in quite different areas of science who were
willing to contribute a chapter within the prescribed schedule. It is with great
satisfaction that I thank all 52 authors from 8 countries for their understanding
and for devoting their time to this effort. Special thanks are due to Dr. F. Boschke
of Springer for his advice and discussions throughout all stages of preparation
of the Handbook. Mrs. A. Heinrich of Springer has significantly contributed to
the technical development of the book through her conscientious and efficient
work. Finally I like to thank my family, students and colleagues for being so
patient with me during several critical phases of preparation for the Handbook,
and to some colleagues and the secretaries for technical help.
I consider it a privilege to see my chosen subject grow. My interest in Environmental Chemistry dates back to my early college days in Vienna. I received
significant impulses during my postdoctoral period at the University of California

and my interest slowly developed during my time with the National Research


Preface

IX

Council of Canada, before I could devote my full time of Environmental
Chemistry, here in Amsterdam. I hope this Handbook may help deepen the
interest of other scientists in this subject.
Amsterdam, May 1980

O. Hutzinger

Twentyone years have now passed since the appearance of the first volumes of
the Handbook. Although the basic concept has remained the same changes and
adjustments were necessary.
Some years ago publishers and editors agreed to expand the Handbook by
two new open-end volume series: Air Pollution and Water Pollution. These
broad topics could not be fitted easily into the headings of the first three volumes. All five volume series are integrated through the choice of topics and by a
system of cross referencing.
The outline of the Handbook is thus as follows:
1.
2.
3.
4.
5.

The Natural Environment and the Biogeochemical Cycles,
Reaction and Processes,

Anthropogenic Compounds,
Air Pollution,
Water Pollution.

Rapid developments in Environmental Chemistry and the increasing breadth of
the subject matter covered made it necessary to establish volume-editors. Each
subject is now supervised by specialists in their respective fields.
A recent development is the accessibility of all new volumes of the Handbook
from 1990 onwards, available via the Springer Homepage inger. de
or or series/hec/.
During the last 5 to 10 years there was a growing tendency to include subject
matters of societal relevance into a broad view of Environmental Chemistry.
Topics include LCA (Life Cycle Analysis), Environmental Management, Sustainable Development and others.Whilst these topics are of great importance for the
development and acceptance of Environmental Chemistry Publishers and Editors have decided to keep the Handbook essentially a source of information on
“hard sciences”.
With books in press and in preparation we have now well over 40 volumes
available.Authors, volume-editors and editor-in-chief are rewarded by the broad
acceptance of the “Handbook” in the scientific community.
Bayreuth, July 2001

Otto Hutzinger


Contents

Foreword
Dušan Gruden . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

XIII

Introduction
Dušan Gruden . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1

Power Units for Transportation
Dušan Gruden, Klaus Borgmann, Oswald Hiemesch . . . . . . . . . . . .

15

Means of Transportation and Their Effect on the Environment
Hans Peter Lenz, Stefan Prüller, Dušan Gruden . . . . . . . . . . . . . .

107

Legislation for the Reduction of Exhaust Gas Emissions
Wolfgang Berg . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

175

Fuels
Dušan Gruden . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

255

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

289

Foreword

Over centuries mankind has pursued technical progress for the benefit of
improved prosperity without simultaneously taking appropriate steps to ensure
the environmental friendliness of the involved processes. However, in the middle of the 20th century environmental episodes drew attention to the negative
impacts on the environment caused by this progress.
As a matter of fact, concern about the influence of human activities on the
environment is neither a new phenomenon nor a new attribute of modern
people but has accompanied human society throughout its existence. What is
new, however, is the increasing intensity of man’s efforts to protect his environment as reflected in a multitude of national and international environmental
laws enacted all around the globe.
Life as a whole, and human existence in particular, are characterized by constant movement and changes. This means that living beings need to be mobile
to survive. By developing suitable technical means man has enormously increased his mobility – expressed in terms of speed and distance – when compared
with other living beings on our planet. The automobile is one of the inventions
that has made a decisive contribution to this mobility and it has become an inseparable part of modern human society. In the second half of the 20th century,
the automobile developed from a luxury article and prestige object for a few into
a basic commodity for millions of people. It is through this widespread use that
negative impacts on the environment have become clearly visible. Therefore,
since the late 1960s and early 1970s, automotive development has been accompanied by an ever increasing number of strict legal standards, e.g., about the
reduction of exhaust gas pollutants, noise emissions, hazardous substances and
waste, as well as about improved recyclability of materials and other aspects.
Achievements in improving the ecological characteristics of the automobile
are highly impressive: A modern car emits only fractions of the amounts of
noise and exhaust gas pollutants produced by its predecessors 30 years ago.
Today, 100 modern passenger cars in total emit less of the legally limited exhaust
gas constituents than one single car of 1970. The same trend can be found with
all the other ecologically relevant automotive features so that the absolute
impact of the automobile on our environment is considerably lower today than
it was in the past.
The development of the automobile is increasingly linked to deliberations

about sustainable development.While this term in the recent past was only related to the aspect of ecological consequences for the environment, it comprises


XIV

Foreword

today at least two further essential pillars, namely economic consequences and
social responsibility.
When discussing sustainability in the context of automotive development, it
must be borne in mind that essential technical elements of the automobile –
such as safety, power output, torque, fuel consumption, durability, maintenance
intervals, and comfort should not be compromised.
The modern automobile has achieved outstanding performance and superiority compared to its predecessors in all theses elements and will continue to
proceed along this evolutionary development path.
This book focuses on ecological aspects related to the development and use
of automobiles, leaving many environment-related initiatives towards improvements of the automotive production process out of consideration. It shall, however, be mentioned in this context that also the production of modern cars is not
possible without the observance of a wide range of stringent environmental
laws. Thus, in order to be allowed to enter the market, a car must not only perform environmental-friendly during its operation but must have been produced
to ecological standards as well. Company audits carried out routinely according
to EMAS (Eco Management Auditing Scheme) and ISO 14001 show that automotive manufacturers are constantly improving the ecological compatibility of
their production processes.
The contributions to this book were written by experts, most of whom have
been actively involved in the development of modern automobiles and their
combustion engines for more than 30 years. They have participated in all phases
of the ecological development of the automobile – from the basic attempts to
respond to the first exhaust gas emission control requirements in the USA
(1966) and Europe (1970) to the cost-intensive efforts towards meeting the comprehensive and highly demanding emission legislations currently existing and
further anticipated worldwide.
As the 20th century ends and the 21st century begins, these experts have summarized their experience and know-how in this book which bears witness to the

successful implementation of ecological considerations into automotive development work.
In my capacity as coordinator of the preparatory work for this book I would
like to thank my colleagues – Prof. Dr. sc. techn. Hans Peter Lenz and his collaborator, Mr. Stefan Prüller (Dipl.-Ing.) of Technical University of Vienna, Dr.
Klaus Borgmann and Mr. Otto Hiemesch (Dipl.-Ing.) of BMW AG and Dr. Wolfgang Berg, Consultant and long-standing collaborator of DaimlerChrysler AG –
for their cooperation and valuable contributions.
I would like to express particular gratitude to Dr. Ing. h.c. F. Porsche AG for
permission to carry out this project.
Weissach, June 2003

D. Gruden


The Handbook of Environmental Chemistry Vol. 3, Part P (2003): 1–15
DOI 10.1007/b 10445

The Diversity of Naturally Produced Organohalogens
Gordon W. Gribble
Department of Chemistry, Dartmouth College, Hanover, NH 03755, USA
E-mail:

More than 3700 organohalogen compounds, mainly containing chlorine or bromine but a few
with iodine and fluorine, are produced by living organisms or are formed during natural abiogenic processes, such as volcanoes, forest fires, and other geothermal processes. The oceans are
the single largest source of biogenic organohalogens, which are biosynthesized by a myriad of
seaweeds, sponges, corals, tunicates, bacteria, and other marine life. Terrestrial plants, fungi,
lichen, bacteria, insects, some higher animals, and even humans also account for a diverse collection of organohalogens.
Keywords. Organohalogen, Organochlorine, Organobromine, Natural halogen

1

Introduction

. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2

2

Sources and Compounds . . . . . . . . . . . . . . . . . . . . . . .

2

2.1
2.2
2.3
2.4
2.5
2.6
2.7
2.8
2.9
2.10

Marine Plants . . . . . . . .
Marine Sponges . . . . . . .
Other Marine Animals . . .
Marine Bacteria and Fungi .
Terrestrial Plants . . . . . .
Fungi and Lichen . . . . . .
Bacteria . . . . . . . . . . .
Insects . . . . . . . . . . . .

Higher Animals and Humans
Abiogenic Sources . . . . .

3

Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . 13

4

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

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© Springer-Verlag Berlin Heidelberg 2003


2

G. W. Gribble

1
Introduction
Thirty years ago some 200 natural organohalogen compounds had been documented (150 organochlorines and 50 organobromines) [1]. Nevertheless, the scientific community generally considered these compounds to be isolation artifacts
or rare abnormalities of nature. For example,“present information suggests that
organic compounds containing covalently bound halogens are found only infrequently in living organisms” [2]. Unfortunately, even today this myth persists and
has entered modern textbooks: “unlike metals, most of these compounds [halogenated hydrocarbons] are man-made and do not occur naturally …” [3].
The striking increase in the number of known natural organohalogens to more
than 3700 is partly a consequence of the general revitalization of interest in natural
products as a potential source of new medicinal drugs. Furthermore, the relatively
recent exploration of the oceans has yielded large numbers of novel organohalogens from marine plants, animals, and bacteria. Much of the success of these explorations is attributed to improved collection methods (SCUBA and remote submersibles for the collection of previously inaccessible marine organisms), selective
bioassays for identifying biologically active compounds, powerful multidimensional nuclear magnetic resonance spectroscopy techniques for characterizing
sub-milligram quantities of compounds, and new separation and purification techniques (liquid-liquid extraction, high-pressure liquid chromatography). Furthermore, an awareness and appreciation of folk medicine and ethobotany have guided
natural product chemists to new medicinal leads. Although most of the biogenic
organohalogens discovered over the past thirty years are marine-derived, many
other halogenated compounds are found in terrestrial plants, fungi, lichen, bacteria, insects, some higher animals, and humans [4–9]. As of June 2002, the breakdown of natural organohalogens was approximately: organochlorines, 2200;
organobromines, 1900; organoiodines, 100; organofluorines, 30 [10].A few hundred
of these compounds contain both chlorine and bromine.

2
Sources and Compounds
2.1
Marine Plants

Seaweeds produce an array of both simple and complex organohalogens, presumably for chemical defense. Some simple haloalkanes found in marine algae
are shown in Fig. 1. Laboratory cultures of marine phytoplankton produce
chloromethane, bromomethane, and iodomethane [11].
The favorite edible seaweed of native Hawaiians is “limu kohu” (Asparagopsis
taxiformis), and this delicacy contains more than 100 organohalogens, most of
which were previously unknown compounds [12, 13]. Bromoform is the major
organohalogen in this seaweed.A selection of others is depicted in Fig. 2.Another
red alga, Bonnemaisonia hamifera, contains several brominated heptanones that
might be precursors to bromoform formed via a classical “haloform reaction”


The Diversity of Naturally Produced Organohalogens

3

Fig. 1. Some haloalkanes produced by marine algae

Fig. 2. Some organohalogens found in the red alga Asparagopsis taxiformis

[14]. Bromoform may serve as an antifeedant and/or antibacterial agent for the
seaweed.
A vast number of halogenated terpenes and the related C15 acetogenins are
produced by marine plants. Nearly 50 species of the red alga genus Laurencia
have yielded hundreds of such compounds; a small selection of recent examples
is shown in Figures 3 and 4 [15–22].
Blue-green algae (cyanobacteria) are the source of a large number of halogenated, mainly chlorinated, metabolites [23]. In particular, Lyngbya majuscula
is prolific in this regard and some recent examples are shown in Fig. 5 [24–27].
The potent anticancer drug candidate cryptophycin A (1) was isolated from
cultures of a Nostoc sp. blue-green alga, and the structurally novel nostocyclophane (2) is produced by Nostoc linckia. A detailed study of the brown alga
Cystophora retroflexa reveals the presence of seventeen halogenated phlorethol

and fucophlorethol derivatives, one of which is the complex 3 [28] (Fig. 6). Synthetic approaches to cryptophycin are discussed later in this volume.
2.2
Marine Sponges

Sponges also rely heavily on chemicals for their survival, and many of these compounds contain halogen. In some cases, it is evident that bacteria or microalgae
associated with the host sponge actually produce the metabolites. Recent exam-


4

Fig. 3. Some Laurencia terpenes

Fig. 4. Some Laurencia C15-acetogenins

G. W. Gribble


The Diversity of Naturally Produced Organohalogens

Fig. 5. Some organohalogens from the blue-green alga Lyngbya majuscula

Fig. 6. Some organohalogens from blue-green and brown algae

5


6

G. W. Gribble

Fig. 7. Some organohalogens from marine sponges

ples of sponge organohalogens include fatty acid derivatives (4) [29], pyrroles (5)
[30], indoles (6) [31], phenol derivatives (7) [32], tyrosine derivatives (8) [33], terpenes (9) [34], diphenyl ethers (10) [35], and even dioxins (11) [36]. These fascinating compounds are illustrated in Fig. 7.
2.3
Other Marine Animals

Ascidians (tunicates or sea squirts), nudibranchs (sea slugs), soft corals (gorgonians), bryozoans (moss animals), and acorn worms all produce a dazzling collection of organohalogens. Some recent examples [37–40] are shown in Fig. 8.


The Diversity of Naturally Produced Organohalogens

7

Fig. 8. Some organohalogens from marine animals

2.4
Marine Bacteria and Fungi

A new thrust of natural product research is the study of marine bacteria and
fungi.A number of novel organohalogens have been discovered in this endeavor,
and recent examples (12–14) [41–43] are shown in Fig. 9. The novel halogenated
bipyrroles 15 and 16, which are found in ocean-feeding sea birds [44–46], are
most likely produced by marine bacteria. These compounds represent the first
case of bioaccumulative natural organohalogens. The related “Q1” (17) has been
discovered in a multitude of marine animals and even in the milk of Eskimo
women who consume whale blubber [47, 48]. This latter scenario represents the
first case of the bioaccumulation of natural organohalogens in humans.
2.5
Terrestrial Plants

By comparison with marine plants, terrestrial plants are relatively devoid of halogenated compounds. However, many notable exceptions do exist. The growth
hormone 4-chloroindole-3-acetic acid (18) and its methyl ester are biosynthesized by peas, lentil, vetch, and fava bean (Fig. 10). Bromobenzene has been detected in the volatiles of oakmoss, and the Thai plant Arundo donax contains the
weevil repellent 19 [49]. Both chloromethane and bromomethane have several
plant sources. Chloromethane is produced by potato tubers [50], and bro-


8

G. W. Gribble

Fig. 9. Some organohalogens from marine bacteria and fungi

momethane, a commercial fumigant and nematicide, is produced by broccoli,
cabbage, mustard, pak-choi, radish, turnip, and rapeseed [51]. The global annual
production of bromomethane by rapeseed and cabbage is estimated to be 6600
and 400 tons, respectively. The authors conclude that “given the ubiquitous distribution of bromide in soil, methyl bromide production by terrestrial higher
plants is likely a large source for atmospheric methyl bromide”. Some recent plant
organohalogens (20–22) [52–54] are shown in Fig. 10. The edible Japanese lily
(Lilium maximowiczii) produces seven novel chlorophenol fungicides in response to attack by the pathogenic plant fungus Fusarium oxysporum at the site
of infection [55].
2.6
Fungi and Lichen

Fungi and lichen produce a variety of organohalogens, from the simple
chloromethane and chloroform to exceedingly complex compounds. The earliest
discovered organohalogen compounds are the chlorine-containing fungal
metabolites griseofulvin, chloramphenicol, aureomycin, caldariomycin,

The Diversity of Naturally Produced Organohalogens

9

Fig. 10. Some terrestrial plant organohalogens

sporidesmin, ochratoxin A, and others. A study of three species of fungi (Caldariomyces fumago, Mycena metata, and Peniophora pseudopini) revealed that
they produce de novo up to 70 µg chloroform L–1 of culture medium per day [56].
The fungus Mollisia ventosa has yielded several calmodulin inhibitors such as
KS-504d (23), which contains 70% chlorine by weight [57]. The novel topoisomerase inhibitors topopyrones A (24) and B (25) were isolated from a Phoma sp.
fungus [58, 59], and a recent study of the white rot fungus Bjerkandera adusta has
yielded bjerkanderol B (26) [60]. Experiments with Na37Cl supplied to the culture
revealed incorporation of 37Cl in 26. The slime mold Dictyostelium purpureum
produces AB0022A (27), which is the first naturally occurring chlorinated dibenzofuran [61]. These fungal metabolites are listed in Fig. 11.
2.7
Bacteria

Bacteria are amazing chemical factories and the resulting synthetic metabolites
often possess astounding structural complexity. More than fifty Streptomyces


10

G. W. Gribble

Fig. 11. Some fungal and lichen organohalogens

species have yielded organohalogen metabolites. The bacterium Amycolatopsis
orientalis produces the life-saving glycopeptide antibiotic vancomycin, which has
been used for nearly 50 years to treat penicillin-resistant infections [62, 63]. The

two chlorine atoms in vancomycin are essential for optimal biological activity.
Recent examples of Streptomyces metabolites (28–31) [64–67] are listed in
Fig. 12.
2.8
Insects

It is well known that insects use chemicals for both communication
(“pheromones”) and defense (“allomones”), but very few of these compounds
contain halogen. A notable exception is 2,6-dichlorophenol, the sex pheromone
of at least a dozen tick species [68]. The German cockroach utilizes two chlorinated steroids as aggregation pheromones [69]. An extraordinary finding is that
chloroform is produced by termites. Six Australian termite species produce chloroform within their mounds up to 1000 times higher than the ambient concentration [70]. The authors conclude that this source may account for as much as
15% of the global chloroform emissions.


The Diversity of Naturally Produced Organohalogens

11

Fig. 12. Some Streptomyces sp. organohalogens

2.9
Higher Animals and Humans

Organohalogens are rare in higher animals. However, several such compounds
have been identified. The Ecuadorian frog Epipedobates tricolor has yielded epibatidine (32), and the iodolactone 33 is present in the thyroid gland of dogs. Recently, several halogenated compounds (34–36) were shown to be products of the
action of human white blood cell myeloperoxidase-induced halogenation on invading pathogens and in various disease processes [71–73] (Fig. 13). This topic
is also the subject of a chapter in this volume. Myeloperoxidase from humans


12

G. W. Gribble

Fig. 13. Some organohalogens from higher animals including humans

converts chlorophenols to chlorinated dioxins and dibenzofurans [74], and thus
a human biosynthesis of dioxins is possible. The conversion of predioxins to
dioxins in rats has been demonstrated [75].
2.10
Abiogenic Sources

Natural combustion sources such as biomass fires, volcanoes, and other geothermal processes account for a wide range of organohalogens. The early studies of volcanic gases and the presence of organohalogens discovered therein by
Stoiber and Isidorov are well documented [4, 6]. A recent study of the volcanoes
Kuju, Satsuma Iwojima, Mt. Etna, and Vulcano has revealed an extraordinarily
large array of organohalogens, including 100 organochlorines, 25 organobromines, 5 organofluorines, and 4 organoiodines, most of which are new compounds [76]. This topic is discussed further elsewhere in this volume. Haloalkanes have been found entombed in rocks, minerals, and shales. Thus, when
rocks are crushed, for example, during mining operations, small quantities of
CH3Cl, CH2Cl2, CHCl3, CCl4, CH3CHCl2, ClCH2CH2Cl, Cl2C = CH2,CH3CH2Br,
CF2Cl2, CFCl3, CHF3, chlorobenzene, 1-chloronaphthalene, and other organohalogens are released [77, 78]. For example, 1000 tons of silvinite ore yields 50 g of
chloroform. The authors estimate that the potassium salt mining industry alone
accounts for the annual liberation of 10,000–15,000 tons of CHCl3 and 100–
150 tons each of CCl4 and CFCl3. Several chlorinated benzoic acids, some chloroalkanes, and other chlorinated aromatics, were found in the meteorites Cold
Bokkeveld, Murray, Murchison, and Orgueil [79, 80].
While there is no dispute about the emissions of chloromethane and bromomethane from biomass burning and other natural sources [81, 82], the evidence regarding larger organohalogens, such as dioxins, has been more difficult
to obtain and quantify [83]. However, numerous recent studies suggest that the


The Diversity of Naturally Produced Organohalogens

13

dioxins in sediments and clays have originated from natural sources [84, 85], and
one such obvious source is biomass burning and subsequent deposition [86, 87].
Moreover, other studies indicate that dioxins are formed in peat and forest soil,
presumably via the enzymatic oxidative dimerization of natural chlorophenols
[88, 89].

3
Concluding Remarks
The incredibly large number of marine and terrestrial organisms that are awaiting exploration for their chemical content virtually guarantees the discovery of
numerous new natural organohalogens, many of which will doubtless have significant biological activity. It also seems highly likely that additional mammalian
organohalogens will be identified and their role in the biodisinfection process
will become understood. The clear and convincing evidence that chlorinated
dioxins and dibenzofurans have several natural sources – both abiogenic and biogenic – is one of the most significant and politically important scientific discoveries of our age.

4
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The Diversity of Naturally Produced Organohalogens

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33:2543


The Handbook of Environmental Chemistry Vol. 3, Part T (2003): 15 – 106
DOI 10.1007/b11992HAPTER 1

Power Units for Transportation
Dušan Gruden 1 · Klaus Borgmann 2 · Oswald Hiemesch 2
1
2

Dr. Ing. h.c. F. Porsche Aktiengesellschaft, Porschestrasse, 71287 Weissach, Germany
E-mail:
Bayerische Motoren Werke Aktiengesellschaft, Hufelandstrasse, 80788 München, Germany

For more than 125 years, gasoline and Diesel engines have prevailed as the exclusive drive unit

in road transportation. None of the other power units invented to date has been able to make
use of the energy content of mineral oil with the piston engine’s same good efficiency.
Combustion is the fundamental process by which the chemical energy of fuels is converted
into thermal energy and further into mechanical work. If hydrocarbon-containing fuels were
completely burnt, the resulting products would be carbon dioxide and water vapor only. Since
it is impossible to obtain a 100% complete combustion the exhaust gases always include a great
variety of combustion products, the most important are: carbon monoxide, unburnt hydrocarbons, nitrogen oxides and particulate matter.
During its 125 years of existence, the Otto (gasoline) engine – as it was called after its inventor – has been developed into a mature combustion engine which is characterized by an excellent efficiency and low pollutant emissions. The properties of the gasoline engine strongly depend
on the composition of the air-fuel mixtures and ignition parameters. The influence of the socalled engine design parameters on combustion and exhaust emission is no less important.
The emission of many of the exhaust-gas constituents can be influenced and minimized at
their place of origin, that is in the combustion chamber by correctly selecting and adapting the
relevant engine design and operating parameters. If optimization of engine-internal parameters for further reducing of the exhaust gas emissions are not enough anymore, so-called engine-external measures must be additionally taken. It was found that so-called three-way catalyst reduces the three aforementioned pollutants by clearly more than 90%, provided that a
precisely stoichiometric A/F-ratio is used.
Thanks to the strict maintenance of a precise stoichiometric air/fuel mixture the three-way
catalyst allows very low HC, CO and NOx pollutant emissions to be achieved. However, in this
operating range, fuel consumption is 8 to 15% higher (with a resulting higher CO2 emission)
than during lean-burn operation.
One of the technically most useful solutions to reduce the fuel consumption and CO2 emission of gasoline engines is to make them tolerate lean air/fuel mixtures. The future of the leanburn gasoline engines will almost exclusively depend on the successful development of NOxexhaust-gas after-treatment technologies for lean air/fuel mixtures.
Diesel engines are internal combustion units with the highest thermal efficiency. Mixture
formation is achieved through high pressure fuel injection. The fuel leads to self-ignition in the
highly compressed air of the engine cylinder. The power and torque characteristics of modern
Diesel engines are comparable with those of spark ignition (Otto) power units of equal capacity, the fuel consumption however is approx. 20% lower.
The Diesel power unit has achieved a high status in transport. The world wide share of Diesel
engines in passenger vehicles is now approx. 20%, whereas in freight transport on the roads and
by water the share is approaching 100%, diesel being the only cost effective alternative.
Increasingly, new methods for injection combustion, exhaust gas recirculation and after
treatment (NOx-Cat, Diesel particle filter) are being pursued to meet the ever stricter emission
legislations, aimed at limiting the effects on the environment.
Ever since its invention, the 4-stroke reciprocating piston engine has been considered as a
rather complex thermal unit which should better be replaced by far less complicated designs.

© Springer-Verlag Berlin Heidelberg 2003


16

D. Gruden et al.

When summing up all the properties required to smoothly operate cars over wide speed and
load ranges and a long lifetime, all alternative concepts have never succeeded in edging the Otto
and Diesel engines out of their top positions. Further optimized versions of gasoline and Diesel
engines will continue to prevail in the automotive domain in the coming 15 to 20 years. Due
to their theoretically high efficiency and low pollutant emissions, fuel cells are among the most
promising alternative energy sources of the future.
Keywords. Combustion process, Otto engine, Gasoline engine, Diesel engine, Fuel/air mixture,
Power output, Fuel consumption, Exhaust gas emission, Carbon monoxide, Unburnt hydrocarbons, Nitrogen oxides, Particulates, Operating parameter, Design parameter, Ignition, Injection,
Compression ratio, Combustion chamber, Valve timing, Exhaust gas after-treatment, Catalyst,
Particulate filter, Turbo charging, 2-stroke engine, Alternative engine, Fuel cell, Hybrid drive

1

Combustion Fundamentals and Combustion Products
(D. Gruden) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

1.1
1.2
1.3
1.4
1.5
1.6

General Issues . . . . . . . .
Carbon Monoxide (CO) . .
Unburnt Hydrocarbons (HC)
Nitrogen Oxides (NOx) . . .
Particulate Matter (PM) . .
References . . . . . . . . . .

2

The Otto (Gasoline) Engine (D. Gruden)

2.1
2.2
2.3
2.4
2.4.1
2.4.1.1
2.4.1.2
2.4.2
2.4.2.1
2.4.2.2
2.4.3
2.5
2.5.1
2.5.1.1
2.5.1.2
2.5.1.3
2.5.1.4
2.5.2
2.5.2.1

2.5.2.2
2.5.2.3
2.6

General Issues . . . . . . . . . . . . . . . . . . . . . . . . . . .
Power Output and Fuel Consumption . . . . . . . . . . . . . .
Exhaust Gas Emission . . . . . . . . . . . . . . . . . . . . . .
Engine-Internal Measures for Pollutant Reduction . . . . . . .
Operating Parameters . . . . . . . . . . . . . . . . . . . . . .
Air-Fuel Mixture . . . . . . . . . . . . . . . . . . . . . . . . .
Ignition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Design Parameters . . . . . . . . . . . . . . . . . . . . . . . .
Combustion Chamber Shape . . . . . . . . . . . . . . . . . . .
Compression Ratio . . . . . . . . . . . . . . . . . . . . . . . .
Limitation of Pollutant Reduction by Engine-Internal Measures
Engine-External Measures for Pollutant Reduction . . . . . . .
Fuel-Independent Measures . . . . . . . . . . . . . . . . . . .
Secondary Air-Injection . . . . . . . . . . . . . . . . . . . . .
EGR (Exhaust-Gas Recirculation) . . . . . . . . . . . . . . . .
Portliners . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Thermal Exhaust-Gas After-Treatment . . . . . . . . . . . . .
Fuel-Dependent Measures . . . . . . . . . . . . . . . . . . . .
Oxidation Catalyst . . . . . . . . . . . . . . . . . . . . . . . .
Reduction Catalyst . . . . . . . . . . . . . . . . . . . . . . . .
3-Way Catalyst Plus Oxygen Sensor . . . . . . . . . . . . . . .
The Lean-Burn Engine – the Ultimate Target of Otto-Engine
Development . . . . . . . . . . . . . . . . . . . . . . . . . . .
Problems of Lean-Burn Operation . . . . . . . . . . . . . . . .

2.6.1

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