Decontamination of Warfare Agents: Enzymatic Methods for the Removal of B/C Weapons

312 Pages·2008·3.12 MB·English

Decontamination of Warfare
Agents
Edited by
André Richardt and
Marc-Michael Blum
Further Reading
N. Khardori (Ed.) H.-J. Jördening, J. Winter (Eds.)
Bioterrorism Preparedness Environmental Biotechnology
Medicine – Public Health – Policy Concepts and Applications
2006 2005
ISBN: 978-3-527-31235-1 ISBN: 978-3-527-30585-8
Decontamination of Warfare Agents
Enzymatic Methods for the Removal of
B/C Weapons
Edited by
André Richardt and Marc-Michael Blum
The Editors All books published by Wiley-VCH are carefully
produced. Nevertheless, authors, editors, and
Dr. André Richardt publisher do not warrant the information
German Armed Forces Institute for Protection contained in these books, including this book, to
Technology – NBC Protection be free of errors. Readers are advised to keep in
Business Area of Biological and Chemical mind that statements, data, illustrations,
Decontamination procedural details or other items may
Humboldtstr. 100 inadvertently be inaccurate.
29633 Munster
Germany Library of Congress Card No.:
applied for
Dr. Marc-Michael Blum
University of Frankfurt British Library Cataloguing-in-Publication Data
Institute of Biophysical Chemistry A catalogue record for this book is available from
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Germany Bibliographic information published by the
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detailed bibliographic data are available in the
Internet at <http://dnb.d-nb.de>.
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ISBN: 978-3-527-31756-1
V
Foreword
The present book is intended to give a comprehensive overview of the history and
state - of - the - art of a novel experimental technique: the enzymatic decontamination
of biological and chemical warfare ( C/BW ) agents. By this, it not only intends to
point out the actual relevance and need of modern technologies, but also tries to
contribute efforts to a better international coordination of promising research and
development work in this fi eld. Decontamination in general defi nes a technical
process used to reduce or ideally remove or destroy contaminants, and moreover,
to prevent the spread of contaminants from persons and equipment. Contamina-
tion with C/BW agents can occur without warning, as a result of attacks and col-
lateral damage during military operations, as well as by deliberate release of highly
toxic materials and infectious agents, or industrial accidents and natural outbreaks
of diseases. Historically, military communities have the highest requirement for
powerful decontamination technologies, not at least presumably because they are
potentially confronted with a higher abundance and severity of C/BW agent attacks
in comparison with possible terrorist or criminal scenarios with localized release
of minor quantities.
The main reason to search for new technologies is that the current decontamina-
tion procedures for C/BW agents depend on higher temperature treatment and
harsh chemical reactive components e. g. strong oxidants and chemical dis-
infectants. These techniques and compounds are often not suitable for different
materials, cause logistic problems and are themselves hazardous, corrosive and
environmentally critical. In many Armed Forces, aggressive and toxic substances
like hypochlorite and formaldehyde are still the pivotal reactive components for
C/BW - decontamination. The common goal of the various decontamination mea-
sures is to rapidly destroy known CW agents as well as to disinfect bacteria, fungi
and protozoa, inactivate viruses and detoxify toxins.
For all decontamination procedures of clothing, material and vehicles, the mili-
tary user would rather prefer a modern technique that is equally effective for CW
and BW agents. However, this approach is technically very ambitious. The decon-
tamination of BW agents including bacterial spores, which are known to be highly
resistant to temperature and disinfectants, represents a particular challenge with
respect to optimizing the proportions of effi ciency and logistic burden, as well as
Decontamination of Warefare Agents.
Edited by André Richardt and Marc-Michael Blum
Copyright © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 978-3-527-31756-1
VI Foreword
its environmental impact. On the other hand, with the search for novel reactive
components, biotechnology- b ased decontaminants became increasingly important
with respect to these requirements. As will be outlined in this book, biotechnologi-
cal approaches based on biochemical catalysis using enzymes on a technical scale
may be competent alternatives or at least additives for existing protection measures
against C/BW agents. They allow decontamination reactions under ambient (mild)
conditions and follow a highly effective catalytic, rather than a reagent- consuming,
stoichiometric principle. The data, as presented here, outline a good prognosis for
such reagents. However, there is also strong evidence that more research and
development efforts in this fi eld – ideally on the basis of internationally coordi-
nated cooperations – are indispensable to effi ciently exploit this valuable biotech-
nology potential for future decontamination techniques, be it for military or civil
defense.
Acting diretor of Bundeswehr
Research Institute of Protection
Technologies – NBC - Protection
VII
Contents
Foreword V
Preface XV
List of Contributors XVII
1 The History of Biological Warfare 1
Friedrich Frischknecht
1.1 Introduction 1
1.2 Pre-Twentieth Century Examples 1
1.3 From World War I to World War II 4
1.4 Secret Projects and Cold War Allegations 5
1.5 Towards the Twenty-fi rst Century: Madmen on the Run 6
1.6 Future Threats – Science or Fiction? 8
1.7 Acknowledgements 8
2 History of Chemical Warfare 11
André Richardt
2.1 Introduction 11
2.2 The Beginning 11
2.3 The Rise of a New Age – From WW I to WW II 12
2.4 The Italian – Ethiopian War 15
2.5 Japanese Invasion of China 15
2.6 The First Nerve Agents 16
2.7 Living with the Danger of Chemical Warfare – From WW II
to 2000 17
2.8 The Running Madmen – Emergence of Chemical Terrorism 18
3 Monitoring and New Threats of Chemical/Biological Weapons 21
André Richardt and Roland Dierstein
3.1 Introduction 21
3.2 International Conventions 21
Decontamination of Warefare Agents.
Edited by André Richardt and Marc-Michael Blum
Copyright © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 978-3-527-31756-1
VIII Contents
3.3 Chemical/Biological Agent Characteristics 26
3.4 Asymmetric Warfare 28
3.5 Threat Scenarios for Chemical/biological Weapons 30
4 Biological Warfare Agents 35
Heiko Russmann and André Richardt
4.1 Introduction 35
4.2 Biological Warfare Agents and Biological Weapons: A Division 35
4.3 Types of Biological Warfare Agents 36
4.4 The “Dirty Dozen” 40
4.4.1 Bacteria 40
4.4.1.1 Anthrax 41
4.4.1.2 Plague 45
4.4.1.3 Tularemia 46
4.4.1.4 Glanders and Meliodosis 46
4.4.1.5 Brucellosis 46
4.4.1.6 Q Fever 47
4.4.2 Viruses 47
4.4.2.1 Smallpox 47
4.4.2.2 Viral Encephalitides 48
4.4.2.3 Viral Hemorrhagic Fevers (VHF Agents) 48
4.4.3 Toxins 49
4.4.3.1 Ricin Toxin 49
4.4.3.2 Botulinum Toxins 49
4.4.3.3 Staphylococcal Enterotoxin B (SEB) 50
5 Chemical Warfare Agents 55
Alexander Grabowski, André Richardt and Marc-Michael Blum
5.1 Introduction 55
5.2 Chemical Warfare Agents and Chemical Weapons: A
Differentiation 55
5.3 Classifi cation 56
5.3.1 Nerve Agents 57
5.3.2 Vesicants 59
5.3.3 Pulmonary Agents 61
5.3.4 Blood Agents 62
5.3.5 Riot Control Agents 63
5.3.6 Psycho Agents 64
5.4 Summary 65
6 Decontamination of Biological Warfare Agents 67
Bärbel Niederwöhrmeier and André Richardt
6.1 Introduction 67
6.2 Resistance of Spores Against Stress and Basics of
Inactivation 67
Contents IX
6.3 Technical Methods for Decontamination of Spore Infested
Buildings 69
6.3.1 Ethylene Oxide 70
6.3.2 Chlorine Dioxide Gas 70
6.3.2.1 Description of the Technology 71
6.3.2.2 Applications for Chlorine Dioxide 72
6.3.2.3 Fumigation of Spore Infested Buildings 72
6.3.3 Formaldehyde Solution or Gas 74
6.3.3.1 Description of the Technology 74
6.3.3.2 Technical Maturity 74
6.3.3.3 Applications of the Technology 75
6.3.3.4 Concerns for the User 75
6.3.4 Vapourized Hydrogen-Peroxide (VHP) 75
6.3.4.1 Description of the Technology 76
6.4 Is Clean Clean Enough or How Clean Is Clean Enough? 78
7 Decontamination of Chemical Warfare Agents 83
Hans-Jürgen Altmann and André Richardt
7.1 Introduction 83
7.2 Defi nition of Decontamination 83
7.3 CW-Agent Decontamination 84
7.3.1 Water and Water Based Decontaminants 85
7.3.1.1 Water 85
7.3.1.2 Water-Soluble Decontamination Chemicals 85
7.3.2 Non-Aqueous Decontaminants 87
7.3.3 Macro- and Microemulsions 89
7.3.3.1 Macroemulsions 89
7.3.3.2 Microemulsions 91
7.3.4 Foams and Gels 92
7.3.4.1 Foams 92
7.3.4.2 Gels 94
7.3.5 Selected CW-Agents and Decontamination Reaction Mechanisms 94
7.3.5.1 Sulfur Mustard (HD) 94
7.3.5.2 Sarin (GB) 95
7.3.5.3 Soman (GD) 96
7.3.5.4 VX 97
7.4 Decontamination Procedures 99
7.4.1 Generalities 99
7.4.2 Equipment Decontamination 100
7.4.2.1 Wet Procedures 100
7.4.2.2 Dry Procedures 107
7.4.3 Clothing and Protective Clothing 107
7.4.4 Decontamination of Personnel 109
7.4.4.1 Hasty Decontamination of Personnel and Personal Gear 110
7.4.5.2 Thorough Decontamination of Personnel 112
7.5 Summary and Conclusions 113
X Contents
8 A Short Introduction to Enzyme Catalysis 117
Marc-Michael Blum
8.1 Introduction 117
8.2 Thermodynamic Equilibrium, Reaction Velocities and the Need for
Catalysis 117
8.3 Proteins and Structure – A Prerequisite for Enzyme Function 120
8.4 From Ligand Binding to Enzyme Activity 126
8.5 Enzyme Classifi cation 130
8.6 Kinetics of Enzyme Reactions 131
8.7 Enzymes for Industrial Applications 133
9 Hydrolytic Enzymes for Chemical Warfare Agent Decontamination 135
Marc-Michael Blum and André Richardt
9.1 Problematic Warfare Agents and Pathways for Detoxifi cation 135
9.2 Hydrolysis of Warfare Agents 136
9.3 Early Examples of Enzymatic Decontamination 136
9.4 Current Hydrolytic Enzyme Systems 137
9.5 Squid DFPase 138
9.6 Paraoxonase (PON) 142
9.7 Organophosphorus Hydrolase (OPH) from Pseudomonas diminuta 144
9.8 Organophosphorus Acid Anhydrolase (OPAA) from Alteromonas 148
9.9 Haloalkane Dehalogenase from LinB from Sphingobium
Japonicum 150
9.10 Carrier Systems for Hydrolytic Enzymes 152
9.11 Technical Decontamination with DFPase – An Example 154
9.12 Conclusions and Outlook 156
10 Laccases – Oxidative Enzymes for Bioremediation of Xenotics and
Inactivation of Bacillus Spores 163
Bärbel Niederwöhrmeier, Lars Ostergaard, André Richardt
and Steffen Danielsen
10.1 Introduction 163
10.2 Nomenclature 163
10.3 Distribution of Laccases 164
10.3.1 Distribution in Plants 164
10.3.2 Distribution in Fungi 164
10.3.3 Distribution in Prokaryotes 165
10.4 General Structure, Biochemical and Active Site Properties of
Laccases 165
10.5 Catalytic Mechanism of Laccases 169
10.6 Laccase-Mediator-System (LMS) 169
10.7 Heterologous Expression of Laccases 171
10.8 Laccase Applications 174
10.8.1 Dye Degradation 175
10.8.2 Delignifi cation and Biobleaching 176