Defense Against Bioterror: Detection Technologies, Implementation Strategies and Commercial Opportunities--Proceedings of the NATO Advanced Research Workshop on Defense against Bioterror held in Madrid, Spain from 8 to 11 April 2004 (NATO Security through

Defense against Bioterror Detection Technologies, Implementation Strategies and Commercial Opportunities

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Defense against Bioterror Detection Technologies, Implementation Strategies and Commercial Opportunities

edited by

Dennis Morrison Institute of Engineering Research & Applications, New Mexico Tech, Albuquerque, NM, U.S.A.

Fred Milanovich Lawrence Livermore National Laboratory, Livermore, CA, U.S.A.

Dmitri Ivnitski Institute of Engineering Research & Applications, New Mexico Tech, Albuquerque, NM, U.S.A. and

Thomas R. Austin The Boeing Company, U.S.A.

Published in cooperation with NATO Public Diplomacy Division

Proceedings of the NATO Advanced Research Workshop on Defense against Bioterror: Detection Technologies, Implementation Strategies and Commercial Opportunities Madrid, Spain 8 -11 April 2004 A C.I.P. Catalogue record for this book is available from the Library of Congress.

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Table of Contents PREFACE

9

LIST OF CONTRIBUTORS

13

Strategic Actionable Net-Centric Biological Defense System S. KORNGUTH

17

Natural Toxins: The Past And The Present E. GRISHIN

29

Biological Weapons Inspections- The Iraq Experience E. B. MYHRE

47

Integrated, Secure And Sustainable Disease Surveillance System In Uzbekistan: Aspects Of Laboratory Research Networks F. T. ADILOVA

51

A Network-Ready, Broad Spectrum, Environmental Pathogen Detection System 67 F. P. MILANOVICH, J. DZENITIS, B. J. HINDSON, A. J. MAKAREWICZ, M. T. MCBRIDE, AND B. W. COLSTON Concept Design Of Anautonomous Biological Agent Detector System (Abads) R. BARTON, R. COLLINS, AND R. STARNES

77

Role Of Prototype System Demonstrations In The Development Of Detection-Based WMD Defenses L. BRANDT

91

Validation Testing For Biological Threat Organisms T. L. HADFIELD

105

Development Of Bioaerosol Alarming Detector A. V. WUIJCKHUIJSE, C. KIENTZ, B. V. BAAR, O. KIEVIT, R. BUSKER, M. STOWERS , W. KLEEFSMAN AND J. MARIJNISSEN

119

Biodetection Using Micro-Physiometry Tools Based On Electrokinetic Phenomena 129 R. PETHIG 5

6 Electro-optical Technique For Detection And Identification Of Biological Agents 143 VICTOR BUNIN Detection Of Microbial Cells With Electrooptical Analysis O. V. IGNATOV, O. I. GULIY, V. D. BUNIN, A. G. VOLOSHIN, D. O’NEIL, AND D. IVNITSKI

147

Recent Advances In Electrochemical And Photochemical Transduction Strategies For Immunosensors Based On Electropolymerized Films165 S. COSNIER Technological Platforms Based On Micro/Nanobiosensors As Early Warning Systems For Biological Warfare 175 L.M. LECHUGA, J.TAMAYO, A.CALLE, M. CALLEJA AND C. DOMINQUEZ Catalytic Beacons For The Detection Of DNA And Telomerase Activity199 Y. XIAO, V. PAVLOV, T. NIAZOV, A. DISHON, M. KOTLER AND I. WILLNER Critical Elements Of Biological Sensor Technology For Deployment In An Environmental Network System D. IVNITSKI, D. MORRISON AND D. J. O'NEIL

207

Electrochemical Immunosensor For Detection Of Francisella 221 tularensis P. SKLADAL, Y. SYMERSKA, M. POHANKA, B.SAFAR, AND A. MACEL Biosensors And Nanotechnological Immunochips For The Detection And Monitoring Of Chemical And Biological Agents S. VARFOLOMEYEV, I. KUROCHKIN, A. EREMENKO, E. RAININA 233 AND I. GACHOK Biosensor For Defence Against Terrorism M. MASCINI AND I. PALCHETTI

245

Biosensors And Biomimetic Sensors For The Detection Of Drugs, Toxins And Biological Agents 261 A. P. F. TURNER AND S. PILETSKY Chemical Multi-Sensor Arrays For Liquids Monolithic Integration Using Microelectronic Technology 273 A.BRATOV AND C. DOMINGUEZ

7 Immunochemical Approaches For Rapid Detection Of Biologically Active Compounds 291 B. B. DZANTIEV, A.V ZHERDEV, AND N.A. BYZOVA Multifunctional Liquid-Crystalline DNA Based Biosensing Units Capable Of Detecting Biologically Relevant Compounds 303 YU. M. YEVDOKIMOV Subject Index

335

PREFACE

Instability in warfare arises when offense significantly outstrips defense. After a half century of vaccine and antibiotic successes in the war against infectious diseases, the advantage has shifted back to the pathogen. Infectious diseases are again the leading cause of human mortality worldwide. To compound matters, the possible intentional spread of disease is not only possible but also it is reality. For instance, in the past two decades, the United States alone has had three biological attacks or incidents against civilians: 1984 salmonella, 1999 West Nile-like Virus, and 2001 anthracis. In addition, several foreign natural epidemics (the recent United Kingdom foot and mouth virus pandemic and the mad cow disease outbreak) have shown the potential for both serious economic and political harm. Indeed, the events of 2001 exposed civilization’s vulnerability to the covert introduction of harmful biological agents. Bioterroism and biological warfare employs living agents or toxins that can be disseminated/delivered by infected individuals, insects, aerosols, and by the contamination of water and food supplies. Most biological agents can be thousands of times more lethal per unit than the most lethal chemical warfare agents. Unlike chemical agents, biological agents attack people stealthily with no observable reaction until after an incubation period (days to weeks). Current disease surveillance and response systems rely on post-symptomatic reporting. However, many infectious agents such as smallpox have a long latency to clinical symptoms, thereby eluding early detection potentially resulting in widespread, uncontrolled contagion. Consequently, the threat of deliberate dissemination of biological agents is the most complicated and problematic of the weapons of mass destruction facing mankind today. 9

10 This volume contains papers presented at the NATO Advanced Research Workshop “Defence against Bioterror: Detection Technologies, Implementation, Strategies and Commercial Opportunities” held at the Hotel Wellington, Madrid Spain from 26 May to 29 May 2004. The objective of the workshop was to contribute to the critical assessment of state-of-the-art of emerging (“breakthrough”) biosensor technologies that will allow for the rapid identification of biological threat agents in the environment and human population; to identify directions for future research, and to promote close working relationships between scientists from different countries and with different professional experience. The volume is devoted to a comprehensive overview of the current state of biological weapons threat; challenges confronting biodetection technologies and systems; ongoing research and development; and, future requirements. Following the structure of the NATO Advanced Research Workshops, the special section starts from the threat overview and current art, then followed detection platforms, networked alarm-type biodetector systems, implementation strategies, electro-optical and electrochemical biosensors. A strategy and commensurate technology to detect a bioagent release at the earliest moment is an essential element of a defense against bioterrorism. The strategy should include: (1) systems of networked biodetectors that provide wide area monitoring for the early warning of a bioagent release; (2) a medical surveillance system that provides early (detection of the presence of disease in the population at large; and, (3) a concept for integrating these technologies into the public sector. In (1) the development of networked alarm-type biodetection systems is extremely important for detecting, tracking and responding to threats. By fielding a network of alarm-type biodetectors, civilian and military defense officials can obtain early warning in the event of a biological attack. The networked alarm-type biodetectors will provide generic discrimination, i.e., pathogenic vs. non-pathogenic bacteria and may be used as a “trigger” for a more sophisticated detector/identifier system. A desired performance requirement of networked alarm-type biodetectors is real-time, pre-exposure detection, discrimination, and identification of biological threats. The sensing element should be able to detect the presence of biological agents at below threshold concentrations in 5-10 min and be sensitive to a broad range of bioagents (multiplex capable). Obviously the incorporation of all these features within one biodetector based on current technology is a very complicated task. Most commercially available biodetectors are inherently bulky, utilize complex instrumentation, multistep assays and other time consuming procedures. The solution may be based on application of new emerging sensor technologies such as array-based biochips, liquid arrays, artificial olfaction and microfluidic systems, ion-channel switches and magnetoresistance technology. In (2) a science base that will provide for

11 biomarkers in human body fluids that indicate the presence of disease must be established. These markers must be able to distinguish pathogen type and be present at the very onset of disease (presymptomatic). Once established, detection technologies and application strategies need to be developed to bring presymptomatic detection to practical application. (3) strategies need to be developed to bring these advances to the public. Indeed, all levels of government are seeking to improve their capability for dealing with the effects and consequences of a biological incident or attack. In particular, cities recognize that their personnel will play a major part in a bioterrorist attack. Each small community is faced with the daunting problem of developing a bio-terrorism response plan with limited resources and limited local expertise. Transportation bioterror security presents an extremely complex problem (alarms, indications, situational awareness, level of response, large probability of false positive detection, effectiveness/performance, cost, politics, limited protection). No accurate and rapid “silver bullet” technology or system in existence can meet this challenge., We recommend the continued development of sensing technologies and the approach of employing multiple, layered detection systems with orthogonal technologies. Biological Warfare Agent (BWA) sensor for defense purposes may also be designed to offer “dual use” capability in the civil sector, including public health environmental air and water monitoring as well as drug discovery. Approach and preparation for biological terrorism can be compared to existing civilian methods for earthquake protection – very low probability of occurrence but with very high consequence. Continued collaboration among NATO members is recommended due to risk of BWA attack against both existing member countries (USA, UK and others) as well as emerging member countries (Russia). We would like to acknowledge the NATO Science Committee for their contributions. Special acknowledgement goes out to Cynthia Hernandez for providing technical document production and preparing the camera-ready version of the text.

The editors: Dennis Morrison, Fred P Milanovich, Dmitri Ivnitski, and Tom R Austin

LIST OF CONTRIBUTORS Dennis Morrison Institute of Engineering Research & Applications 901 University Blvd. SE Albuquerque, NM 87106 USA Phone 505 272 7235 Fax 505 272 7203 [email protected] Fred P. Milanovich Lawerence Livermore National Labs 7000 East Avenue -174 Livermore, CA 94550 USA Phone 925 422 6838 Fax 925 422 8020 [email protected] Tom R. Austin The Boeing Company 2201 Seal Beach Blvd MC 110-SC45 Seal Beach, CA 90740 USA Phone 562 797 3798 Fax 562 797 4778 [email protected] Shawn H . Park The Boeing Company 5301 Bolsa Ave MC-H013-B319 Huntington Beach, CA 92657 USA Phone: 704 896 1606 Fax: 704 896 6417 [email protected] John C Stammreich The Boeing Company 2201 Seal Beach Blvd MC-110-SA32 Seal Beach, CA 90740 USA Phone 562 797 3252 Fax 562 797 4778 [email protected] Oleg VIgnatov Institute of Biochemistry & Physiology of Plants & Microorganisms Russian Academy of Sciences Entuziastov av.,13 Sartov, 410049 Russia Phone 7 8452 970 383 Fax 7 8452 970 383 [email protected] Dmitri Ivniski Institute of Engineering Research & Applications, New Mexico Tech 901 University Blvd. SE Albuquerque, NM 87106 USA Phone 505 272 7255 Fax 505 272 7203 [email protected] Laura M Lechuga Biosensor Group Centro nacional de Microelectronica (IMM-CNM-CSIC) Isaac Newton , 8 28760 Tres Cantos (PTM) Madrid, Spain Phone 34 91 806 0700 Fax 34 91 806 0701 [email protected] Anthony. Turner 13

14 Cranfield University Silsoe Bedfordshire, MK45 4DT UK Phone 44 0 1525 863005 Fax 44 0 1525 863360 [email protected] Steven Kornguth Institute of Advanced Technology 3925 West Braker Lane Suite 400 Austin, TX 78759 USA Phone 512 232 4486 Fax 512 471 9103 [email protected] Robert G. Barton Midwest Research International 425 Volker Blvd. Kansas City, MI 64110 USA Phone 816 360 5268 Fax 816 531 0315 [email protected] Larry D. Brandt Sandia National Laboratories PO Box 969 MS 9201 Livermore, CA 94551 USA Phone 925 294 2969 Fax 925 294 1559 [email protected] Andrey Bratov Centro Nacional de Microelectronica Campus UAB. Bellaterra E -08193 Cerdanyola del Valles Barcelona, Spain Phone 34 93 594 77 00 Fax 34 93 580 14 96 [email protected] Victor D. Bunin State Research Center of Applied Microbiology Obolensk Moscow region, 142253 Russia Phone 7 0967 705716 Fax 7 0967 705716 [email protected] Fatima T. Adilova Inst. of Cybernetics Academy of Sciences 34, F. Khodjaev str. Tashkent, 700125 Uzbekistan Phone 99871 162 71 62 Fax 99871 162 73 21 [email protected] James M. Clark GL Detection Dstl Porton Down Salisbury SP4 OJQ UK Phone 44 1908 613 405 Fax 44 1980 613 987 [email protected] Bob V. Collins Midwest Research International 425 Volker Blvd. Kansas City, MI 64110 USA Phone 816 360 5322 Fax 816 531 0315 [email protected] Serge Cosnier Laboratory of Organic Electrochemistry and Redox Photochemistry UMR CNRS 5630 Institute of Molecular Chemistry FR CNRS 2607 Batiment Chimie Université Joseph Fourier Grenoble 1 301 rue de la Chimie,BP 53 38041 Grenoble Cedex 9 France [email protected] Boris B. Dzantiev

15 Institute of Biochemistry RAS Leniskii Prospect 33 Moscow, 110971 Russia Phone 7 095 954 2804 Fax 7 095 954 2804 [email protected] Eugene V. Grishin Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry Russian Academy of Sciences Ul. Miklukho-Maklaya, 16/10, 117997 GSP Moscow, V-437 Russia Phone 7 095 3305892 Fax 7 095 3350812 [email protected] Ted L. Hadfield Midwest Research International 1470 T reeland Blvd, SE Palm Bay, FL 32909 USA Phone 321 723 4547 ext. 300 Fax 321 722 2514 [email protected] Jay Lewington Smiths Detection 459 Park Ave Bushey Watford, Herts WD23 2BW UK Phone 44 0 1923 658206 Fax 44 0 1923 658025 [email protected] Marco Mascini Universita di Firenze Sesto Fiorentino Dipartimento di Chimica, Polo Scientifico Via della lastruccia 3 Firenze, 50019 Italy Phone 39 055 457 3283 Fax 39 055 457 3384 [email protected] Sebastain Meyer-Plath Smiths Detection 59 Park Ave Bushey Watford, Herts WD23 2BW UK Phone 44 0 1923 658193 Fax 44 0 1923 221361 [email protected] Michael Moniz Circadence Corporation 4888 Pearl East Circle, Ste. 101 Bolder, CO USA Phone 303 413 8837 Fax 303 449 7099 [email protected] Louis Montulli Midwest Research International 613 Rolling Hills Rd Vista, CA 92081 USA Phone 760 977 9601 Fax 760 598 6488 [email protected] Petr Skladal Masaryk University Kotlarska 2 CZ 61137 Brno Czech Republic Phone 420 5 41129402 Fax 420 5 41211214 [email protected] Ronald Pethig School of Informatics University of Wales, Bangor Dean Street Bangor, Gwynedd LL57 1UT UK Phone 44 1248 382 682 Fax 44 1248 361 429 [email protected] Erling B. Myhre Dept. of Infectious Diseases, University Hospital SE-221 85 Lund Sweden

16 Phone 46 46 17 18 67/17 11 30 Fax 46 56 13 74 14 [email protected] Arjan van Wuijckhuijse Dr. Ir. A.L. van Wuijckhuijse TNO Prins Maurits Laboratory Detection Identification and Analytical Chemistry PO Box 45, 2280 AA Rijswijk, THE NETHERLANDS Phone +31 15 284 3343 Fax: +31 15 284 3963 www.pml.tno.nl Sergey D . Varfolomeyev The M.V.Lomonosov Moscow State University Vorobiovy Gory 1, Bldg. 11 119992 Moscow Russia Phone 7 095 939 3589 Fax 7 (095) 939 5417 [email protected] Itamar Willner The Hebrew University of Jerusalem Jerusalem 91904 Israel Phone 972 2 658 5272 Fax 972 2 652 7715 [email protected] Yuri M. Yevdokimov Head of Laboratory of condensed state of nucleic acids of Engelhardt Institute of Molecular Biology RAS Engelhardt Institute of Molecular Biology RAS Vavilov str. 32 Moscow, 119991 Russia Phone 7 095 135 97 20 Fax 7 095 135 14 05 [email protected]

Part 1

CURRENT PROBLEMS OF CHEMICAL TERRORISM

Chapter 1 PROBLEMS OF CHEMICAL TERRORISM AND WAYS OF ITS OVERCOMING

Christophor Dishovsky Department of Military Toxicology, Military Medical Academy, Sofia , Bulgaria

Abstract:

The main problem connected with chemical terrorism is that, beside chemical weapons, terrorists can use different toxic chemicals from the chemical industry, from agriculture or products of industrial facilities released after the terrorist act. An attack to a chemical plant can instantly liberate a number of different chemicals. Studies should be made on incidents occurring in the facility, during transportation, storage or other processes and these are important points in the preparation for protection against chemical terrorism. An important corner-stone of the anti-terrorist organization in any country is to set a Health & Disaster/Anti Terrorist Acts Management system. Country antiterrorist

protection will be improved by the introduction of a universal

strategy on basic therapeutic trends against chemical terrorism. Chemical terrorism can be responsible not only for the spread of large amounts of toxic chemical compounds, but also for chronic and delayed effects of these agents. Intoxication with small doses of toxic agents is also a possibility used by terrorists. The variety of characteristics of a chemical agent used by terrorists needs demands improvement in the detection, personal protection and decontamination procedures, including that of the medical personnel and equipment. Antidote treatment, with the exception of the medical units and organization of national stockpiling which are adequately supplied for, needs a new and extensive study for new antidotes and for improvement of the medical treatment on the area of the terrorist act.

3 C. Dishovsky et al. (eds.), Medical Treatment of Intoxications and Decontamination of Chemical Agents in the Area of Terrorist Attack, 3–11. © 2006 Springer. Printed in the Netherlands.

4

Problems of Chemical Terrorism and Ways of Its Overcoming

Keywords:

antidotes; Anti Terrorist Management Centers; chemical; chemical industry; chemical weapons; decontamination; delayed effects; detection; terrorism

1.

INTRODUCTION

The main problem connected with chemical terrorism is that, beside chemical weapons, terrorists can use various toxic chemicals from the chemical industry, from agriculture or products of industrial facilities released after the terrorist act. An attack to a chemical plant can instantly liberate a number of different chemicals. Studies should be made on incidents occurring in the facility, during transportation, storage or other processes and these are important points in the preparation for protection against chemical terrorism. An important corner-stone of the anti-terrorist organization in any country is to set a Health & Disaster/Anti Terrorist Acts Management system. Country antiterrorist protection will be improved by the introduction of a universal strategy on basic therapeutic trends against chemical terrorism. Chemical terrorism can be responsible not only for the spread of large amounts of toxic chemical compounds, but also for chronic and delayed effects of these agents. Intoxication with small doses of toxic agents is also a possibility used by terrorists. The variety of characteristics of a chemical agent used by terrorists needs demands improvement in the detection, personal protection and decontamination procedures, including that of the medical personnel and equipment. Antidote treatment, with the exception of the medical units and organization of national stockpiling which are adequately supplied for, needs a new and extensive study for new antidotes and for improvement of the medical treatment on the area of the terrorist act. 2.

DISCUSSION

The main problem connected with chemical terrorism is that beside chemical weapons, terrorists can use different toxic chemicals from the chemical industry, the agriculture or products released from industrial facilities following a terrorist act. An attack on a chemical plant can immediately release a number of different kinds of chemicals [6]. Some differences exist between chemical weapons (CW) and the chemicals released after destruction of a chemical plant following a terrorist act [4]: • industrial chemicals are less toxic than CW, but will be present in much higher quantities for a longer period of time; • contamination with the hazardous industrial chemicals eventually covers a bigger area;

Christophor Dishovsky •

5

CW represent a relatively small number of potential agents; on the contrary - toxic industrial chemicals – tens of thousands; • for the known CWs, relatively simple detection and identification equipment and methods have been developed; the potential variety of industrial chemicals makes the detection process very difficult; • decontamination some times may be a long-lasting and expensive procedure; • the products of the decontamination can also damage the environment; • military protective filters are optimized against CW and BW; some hazardous industrial chemicals are not very well filtered by military filters; The study of the accidents in chemical facilities, during transportation, storage and others, the research of the chemical products, which are produced and stored, are important points in the preparation of the defence against chemical terrorism. An example of such an accident is the explosion at the Union Carbide pesticide manufacturing plant (Dec. 3, 1984), which scattered toxic methyl isocyanate (MIC) over the city of Bhopal, India. During the first few days up to 4000 people died of painful, harrowing deaths [10]. The precise knowledge of the chemicals, produced and stored in the factories, is a necessary condition for modeling of the accidents. However, it should be taken into account that in real conditions and especially when the accidents are accompanied with fire, new toxic compounds may be formed. Such is the case with the fire, which occurred on July 13, 1993 in the "Alen Mak" factory in the town of Plovdiv, Bulgaria. During the GC-MS analysis of the air, soil and various parts of the incident site, over 120 different chemical compounds were identified, some of which identical to the ones present on the premises before the fire, while others had obviously formed during the process of combustion. For a great number of these compounds, toxicological data was not found in the accessible information banks, such as IRIS of EPA and others [5]. United Nations APELL (Awareness and Preparedness for Emergencies at the Local Level) [15] chemical accident database (storing information on about 300 major chemical accidents between 1970 and 1998) shows that: - 38% of the accidents occur with hydrocarbons (fuel gases, fuel liquids, oil, or refined petroleum products); - 15% - explosive industrial chemicals; - 8% - chlorine; - 6% - ammonia; - 6% - industrial acids and bases; - 3% - pesticides and chemical intermediates;

6

Problems of Chemical Terrorism and Ways of Its Overcoming

- 21% - polychlorinated biphenyls (2 %), unspecified chemicals (5%) and others. Hydrocarbon production, storage, transportation and distribution facilities are at the top of the list of potential targets. Some of the more common types of chemicals that could be used as improvised weapons against a community include (data from ATSDR [16]: - eye, skin and respiratory irritants (acids, ammonia, acrylates, aldehydes, and isocyanates); - choking agents (chlorine, hydrogen sulfide, and phosgene); -flammable chemical industry gases (acetone, alkenes, alkyl halides, amines); - aromatic hydrocarbons that could be used as water contaminants (benzene, etc.); - oxidizers for improvised explosives (oxygen, butadiene, and peroxides); - aniline, nitrile, and cyanide compounds that could be used as chemical asphyxiants; - compressed hydrocarbon fuel gases that could be used as incendiaries or simple asphyxiants (liquified natural gas, propane, isobutane); - liquid hydrocarbon fuels that could be used as incendiaries or water contaminants (gasoline, jet fuel); - industrial compounds that could be used as blister agents (dimethyl sulfate), and - organophosphate pesticides that could be used as low-grade nerve agents. According to the conclusions reached by some experts, terrorist acts apply a new strategy in the use of chemical weapons and other chemical agents, i.e.: • the use of low doses of toxic chemicals; • to aim at a delayed and unknown effect of intoxication. Investigations in Bhopal, 20 years later, showed that thousands of Bhopal residents suffered from serious long-term side effects such as blindness, and liver and kidney failure. Estimates of total deaths reach up to 20000. Injuries probably exceeded 100000 [10]. The data from terrorist acts in Matsumoto city and Tokyo underground in Japan are important for the understanding that the consequences of a terrorist act bring long lasting troubles [12, 13]. Some investigations showed that allied troops had been exposed to sarin during the first Gulf War and that might have caused the development of the “Gulf war syndrome” in some of the exposed soldiers [7 ]. The main problems caused by OPC are neuro-toxic delayed effects [8]. Shulga [14] suggested also the presence of delayed neuro-endocrine toxicity after intoxication with such compounds. Planning and preparation of anti terrorist measures should be focused on the following specific points [4]: • risk assessment for the use of chemical agents as terrorist agents with particular attention to toxic industrial chemicals and toxins;

Christophor Dishovsky •

7

update assessment of the effective toxic levels that should cover both the known chemical weapons in view of the modern technologies of their use and toxic compounds and chemicals of industrial origin; • inventory and assessment of the available means for medical treatment of chemical intoxications; assessment of the required amounts and types of antidotes (in view of the broader range of potentially toxic agents) and their update with development and introduction of new compounds; • modernization and optimization of individual protection with particular focus on respiratory protection and protective clothing; • creation of new National Pharmaceutical Stockpile, which ensures the availability of medicines, antidotes, medical supplies and medical equipment necessary to counter the effects of biological pathogens and chemical agents; • creation of effective system of information and supply to the site of the terrorist act; • assessment of the available means for indication and control of chemical contamination and the effectiveness of decontamination. It should include a broader range of potentially toxic agents and the available state-of-the-art technologies; • acquires particular significance for the readiness of all levels of civil institutions and the army to counteract chemical terrorism. It should incorporate and implement the latest achievements of computer simulation and virtual reality technologies; • intensive education and training of first responders and physicians is needed for meeting the medical challenges imposed by chemical and other weapons of terrorism. A country’s antiterrorist protection system should also incorporate a general State Strategy against chemical traumatism and terrorism [11]: • medical chapter; • universal program for diagnosis and treatment; • organizational and medical program; • social and informative chapter; • social information regarding chemical traumatism; • knowledge on chemical traumatism and terrorism. Investigations of Wetter et al. [17] showed that hospital emergency departments generally are not prepared to treat victims of chemical or biological terrorism. Some countries have introduced a Health & Disaster/Anti Terrorist Acts Management system, which includes: • Health & Disaster Anti Terrorist Management Centers. They can be a structure of already existing facilities – for example - of the Civil Defense. Some countries created new independent structures. Such centers could act independently, their task being to manage the situation after disasters or terrorist acts. • Facilities for indication of toxic chemicals;

8

Problems of Chemical Terrorism and Ways of Its Overcoming •

Stationary centers for indication of toxic chemicals that work online and are connected to the Health & Disaster Anti Terrorist Management Centers. • Mobile facilities for indication of toxic chemicals for investigating a potential area of a terrorist act. • Regional Medical Centers. They can be Primary or Secondary – depending on the size and type of organization. These can be district hospitals with developed emergency units. • Poison information centers. Regional Medical Centers can play this role. • Mobile Medical units with Clinic for First aid treatment; Laboratory & Diagnostic units; operating theater; hospital, specifications for treatment of patients affected by chemical agents (indication, decontamination). • Satellite communications; • Independent energy supply; • Mobile decontamination facilities; • Training Centers (Center) for Mass Casualties Events. This system will have a dual function. It will enhance not only emergency preparedness, antiterrorist activity but also the public health system. Such a view is suggested by Marmagas et al.[10] about possible connection between preparedness against biological terrorism, public health infrastructure, chronic disease and environmental health tracking network. With a view to improve the level of security of the population from incidents and disasters, a Scientific Coordination Council was created in Bulgaria as an adjunct to the Permanent State Commission for Protection of the Population from Disasters and Incidents [5]. Attached to the Council are several expert committees which organize and conduct research and analysis, give expertise and make risk assessments for nuclear security, radiation, chemical and biological defense, emergency, seismic danger, meteorological and hydrologic problems and physical steadiness, suggest measures for securing and protecting objects which may add to the dangerous conditions. One of the first tasks of the Expert Committee for Chemical Defense was to identify the dangerous chemical conditions on the territory of Bulgaria. At present over 3400 chemical substances are produced in Bulgaria, among which mineral fetilizers, plastics, drugs, and others. The basic criteria for the assessment concern the quantity of reserve of industrially dangerous chemical compounds and compounds which form during fires or through the reactions of these compounds. The classification is also concerned with the existence of storage facilities, product conductors, transportation communications, and others, where risky situations, including terrorist actions, may be expected. The criteria for the above mentioned analysis may be defined as follows [5]: • research of the object as a potential danger; • analysis of the possible terrorist act;

Christophor Dishovsky •

9

analysis of the available system for defense, security and protection; • development of a project for improvement of a new system for defense, security and protection; • organizing of the defense, security and protection of some chosen objects, and consideration and use of the experience; • coordination of the efforts of the various departments, ministries and others in solving the problems of defense, security and protection of the potentially dangerous objects. The country’s antiterrorist preparedness will be improved with the introduction of a universal doctrine (strategy) suggested from Monov [11], with the basic therapeutic trends against chemical terrorism which includes mainly: • antidotes; • detoxication; • reanimation-substitution and correction; • immunobiological activity; • antiviral and antibacterial activity; • organoprotective activity. A great number of severely injured people, after using organophosphorus compounds (OPC) like sarin for example, will need skilled medical help, enough antidotes, preparedness for decontamination and medical equipment such as breathing apparatuses or supplied air-line respirators. Some ideas exist how to solve these problems. In the Military Medical Academy, Sofia, a special antidote, which can be used after fires and a buddy aid antidote – for severe cases of intoxication were created. It can be introduced also as the first and buddy aid antidote. This antidote was prepared in ampoule form bearing the name NEMICOL 5T [9]. It is a multi component preparation which was tested with animals. The investigations show that this antidote very quickly recovers the breathing, the arterial pressure and the EKG in the intoxicated animals. The anticonvulsant activity was very strong and was demonstrated also with EEG experiments. Neuromuscular transmission blocked after OPC intoxication recovered 1-3 minutes after introduction of the Nemicol 5T. All investigated parameters stayed very stable. Cowan et al. [1, 2] suggest the Multi-Threat Medical Countermeasure (MTMC) hypothesis – investigations for developing a single countermeasure drug with efficacy against different pathologies caused by multiple classes of chemical agents. Serine protease inhibitors can prolong the survival of animals intoxicated with the nerve agent soman and can also protect against vesication caused by the blister agent sulfur mustard. Poly (ADP-ribose) polymerase (PARP) inhibitors can reduce both soman-induced neuronal degeneration and sulfur-mustard-induced epidermal necrosis. Accordingly, the drugs with antiinflammatory action against either nerve or blister agent might also

10

Problems of Chemical Terrorism and Ways of Its Overcoming

display multi-threat efficacy for the inflammatory pathogenesis of both classes of chemical warfare agent [1,2]. 3.

CONCLUSION

Nowadays, terrorists have changed their tactics. Beside chemical weapons, they may use different toxic chemicals produced by the industry, the agriculture or failures in the industrial facilities during transportation, storage, fires and the like. They may take advantage also of the application of low doses of toxic chemicals which can provoke delayed and unknown effects of the intoxication. Thorough studies of the chemical products, investigations of the incidents in chemical factories, storehouses and transportation dealing with chemical products are important points in the protection plan against chemical terrorism. A country’s antiterrorist preparedness should include also a State strategy against chemical traumatism and terrorism. The elaboration of Organization of Health & Disaster/Anti Terrorist Acts Management system is an important part of this preparedness. The scientific research in the field of toxicology gains new dimensions and priorities. The introduction of a universal strategy for the basic therapeutic trends against chemical terrorism is necessary. REFERENCES 1.

2. 3. 4.

5.

6. 7.

Cowan F. M., Broomfield C.A., Lenz D. E., Smith W. J., Putative role of proteolysis and inflammatory response in the toxicity of nerve and blister chemical warfare agents: implications for multi-threat medical countermeasures. J. Applied Toxicology, 2003, 23, 3, 177-86. Cowan B. S., Broomfield C. a., Stojiljkovic M. P., Smith W. J., A Review of Multi-Threat Mrdical Countermeasures against Chemical Warfare and Terrorism, Military Medicine, 2004, 169, 11, 850-55. Dishovsky C., “The problems of Chemical Terrorism.” In Technology for Combating WMD Terrorism, Peter J. Stopa, Zvonko Orahovec, ed’s, NATO Science Series, Kluwer Academic Publishers, 2004. Dishovsky C., “The problems of Chemical and Biological Terrorism.” In Medical Aspects of Chemical and Biological Terrorism – Biological Terrorism and Tramautism, Alexander Monov and Christophor Dishovsky, eds, Publishing House of the Union of Scientists in Bulgaria, 2004. Dishovsky C., Belokonsky I., Panchev N., The problems of defence in chemical industryresults of special investigation. Proceedings of the CB Medical Treatment Symposium Industry I; 1998 October 25-31; Zagreb-Dubrovnik, Croatia, MOD of Croatia, 1999, 6973. Eifried G., Terrorism against chemical plants:hazards and risks. Proceedings of the CB Medical Treatment Symposium Industry I; 1998 October 25-31; Zagreb-Dubrovnik, Croatia, MOD of Croatia, 1999, 84-88. Haley, R.W., and Kurt, T.R., Self-reported exposure to neurotoxic chemical combinations in the Gulf War, J. Am. Med. Assos., 1997, 277,231-37.

Christophor Dishovsky 8. 9. 10. 11.

12. 13. 14.

15. 16. 17.

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Haley, R., W., Billecke, S., S., and La Du, B., N., Association of low PON1 type Q (type A) arylesterase activity with neurological symptom complexes in Gulf War veterans, Toxicol. Appl. Pharmacol., 1999, 157, 227-33. Kotev G., DSc Work , Military Medical Academy, Sofia, 1973. ( in Bulgarian ). Marmagas S.W., Kind L. R.,Public Health’s Response to a changed World: September 11, Biological Terrorism, and the Development of an Environmental Health Tracking Network. Amer. J. of Public Health, 2003, 93, 8, 1226-30. Monov Alexander, “Biological Traumatism and Terrorism – unified Medical and Organizational Doctrine”. .” In Medical Aspects of Chemical and Biological Terrorism – Biological Terrorism and Tramautism, Alexander Monov and Christophor Dishovsky, eds, Publishing House of the Union of Scientists in Bulgaria, 2004. Morita, H., Yanagisawa, N., Nakajima, T., et al., Sarin poisoning in Matsumoto, Japan, Lancet, 1995, 346, 290-93. Ohbu, S., Yamashina, A., Takasu, N., et al., Sarin poisoning on Tokyo subway. South. Med. J., 1997, 90, 587-93. Shulga V., “Delayed neuro-endocrine toxicity indused by organophosphorus compoundsnatural consequence of poisonous substances application for terrorist purpose”, In Medical Aspects of Chemical and Biological Terrorism –Chemical Terrorism and Tramautism, Alexander Monov and Christophor Dishovsky, eds, Publishing House of the Union of Scientists in Bulgaria, 2005 ( in press). United Nations APELL (Awareness and Preparedness for Emergencies at the Local Level) http://www.uneptie.org/pc/apell/. U.S. Department of Health and Human Services, Agency for Toxic Substances and Disease Registry (ATSDR) http://www.atsdr.cdc.gov/about.html. Wetter D.C., Daniell W. E., Treser C. D., Hospital preparedness for victims of chemical or biological terrorism. Amer. J. of Public Health, 2001, 91, 5, 710-1

1

A SUMMARY OF THE DISCUSSIONS

Paul Tempest Director of Windsor Energy Group and Vice President of the British Institute of Energy Economics

An emerging energy demand/supply imbalance The IEA expect global energy demand to rise by 66% by 2030 with 90% of the increment supplied by fossil fuels, mainly oil. The Gulf oil producers, holding two thirds of total global proven oil reserves, would have to account for most of this increment and for the replacement of depleting production elsewhere. Such a doubling or even tripling of Gulf oil production capacity would require a massive infusion of external capital and new technology. This looks in present circumstances to be highly unlikely, given the degree of political turbulence in the area, the reluctance of the capital and financial markets to take on such risks and the determination of several governments to protect their own national companies to the point of failing to provide adequate incentives for the international oil companies to participate fully.

“The end of cheap oil” Competition for Gulf oil exports is therefore likely to be intense with South-East Asia taking the bulk and an increasing share. US expectations that US oil imports will double to 24 mbd by 2030 will further distort the market and can only be achieved at the cost of denying supply to the developing world. Oil prices have remained broadly within the US$22-28 OPEC band for the last four years and are now moving beyond the upper limit. Yet industry 3 H. McPherson et al. (eds.), Emerging Threats to Energy Security and Stability, 3–8. © 2005 Springer. Printed in the Netherlands.

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estimates of the global clearing price for oil is mainly within the US$ 16-18 range, implying that the difference is an anxiety premium caused mainly by political turbulence in the Middle East.

Dangerous impacts on the global economy - a nonsustainable energy prospect Periods of high oil prices have always had adverse impacts on global economic growth, just as low oil prices have always acted as a stimulus. Already, continuing high oil prices are seen to be hindering growth for later this year. Whereas the rest of OECD (Organisation for Economic Cooperation and Development) industrialised countries are partly shielded by the weakening of the US $, the impact on the US economy, which is already slowing, and on most developing countries could be severe. One quarter of the world population has no access to electricity and many more rely on wood, residues and dung for cooking and heating. Even on assumptions of the persistence of the average GNP growth over the last 25 years, the number of people without access to electricity is 2030 is unlikely to be below the current level. The steeper the economic rollercoaster caused by oil price spikes, the less chance there will be to reach the IEA target of 75 million new connections per year and the greater the likelihood that global energy poverty will increase rather than decrease.

Changes in oil market leadership Russia (9.0 mbd this year) has overtaken Saudi Arabia and the USA (each about 7.8 mbd this year) as the leader in oil production. Iraq is widely thought to be capable of producing 4-5 mbd by 2010 and possibly 15-20 mbd by 2030. Many of the discussions pivoted around the issue of political stability in Russia and Saudi Arabia. Most contributors considered the IEA assumption of a rapid rise in Saudi production to 19 mbd to be highly unlikely, and indeed, an industry report which is soon to be published predicts the contrary: imminent collapse. Yet the consensus view, although vigorously challenged, was that Saudi Arabia would remain the indispensable provider of surge capacity until 2010 at least.

5

China (5.7 mbd) has outstripped Japan as the second largest oil consumer. Chinese oil imports are predicted to rise from 2mbd in 2003 to 6 mbd in 2010 and 15-20 mbd by 2030.

Iraq approaching “boil-over” Despite considerable and mainly unsung progress in restoring Iraq’s economic infrastructure over the past six months, the projected transition to Iraqi control at mid-04 looks precarious unless the proposals are endorsed by the 60% Shi’a majority (see Special Session C). The possibility of a break-up of Iraq, whether sooner or later, becomes clearer. In the light of this eventuality, a serious contingency plan is needed. “While there are now no known national threats to the boundaries of the USA or Europe, there is no boundary to the global threat of Al-Qaida and other international terrorist organisations. Our defence forces are largely equipped for Cold War needs, not for the rapid-response needs we now face.”

Technology transfer stifled The International Oil Companies provide a rapid and efficient transfer of petroleum technology and effective management where they are permitted to operate. Many oil and gas-producing countries overprotect their national companies to the point of denying IOC access on commercial terms.

The Caucasus impasse Rivalries between the USA, Russia and the EU overshadow efforts by the Caucasus States to develop export capacity for their oil and gas. Political meddling and attempts from outside to control the economy of the region explain the numerous development delays.

6

North African surprises Rapid development of North African oil and gas resources following political détente may alleviate the competitive weakness of Europe in securing adequate imported oil and gas. Sanctions on Libya have been easy to impose, most difficult to dismantle. US policy is still based on a “waitand-see” step-by-step policy as Libya demonstrates compliance.

UK energy policy There is little sign of contingency planning as the UK returns to net gas import dependence (2005-6) and oil import dependence (2010) and coal imports (currently 50% of consumption) continue to rise. Nuclear capacity will also have run down sharply by 2010. UK Government expectations that wind-power will be able to provide 10% of UK electricity may be exaggerated.

Threats to ships Shipping of crude oil and products, which are equivalent to 57% of global oil production, is vital to the global economy, vulnerable to terrorists and the problems are poorly understood. Some 90,000 ships move 2,000mn tons pa. The fleet of LNG carriers is likely to triple within 10-15 years and are getting larger – in the next generation of carrier, they will be 150,000 tons each. A vapour cloud from a damaged LNG vessel will, on ignition, have the impact of detonating a hydrogen bomb. The main hazards are: Ship-seizure by pirates who then transfer and sell the cargo, disguise the ship and ransom the crew. SAS simulations indicate that fewer than 8 minutes would be needed for regaining control of a captured vessel between touching the ship’s side and taking over the bridge. x Ramming – this mostly occurs close to shore and often causes massive spills and pollution. x Infiltration of Ship by terrorist cell working among crew.

7

x Actions by environmental groups (e.g. the seizure of The Brent Spar by Greenpeace) The four most dangerous choke-points for the oil trade are Hormuz (15.5mbd), Malacca Straits (10.5 mbd), Bab al-Mandab (3.3 mbd) and the Suez (0.8 mbd). Collision in congested waterways is not uncommon: in 2 months recently the IMO reported 8 collisions in the Malacca Straits which, along with Indonesia, heads the IMO list of 445 piracy attacks in 2003. This session examined detailed studies of the impact of a blockage of the Malacca Straits, which might be closed from 3 weeks to 3 months adding 3-5 days to voyage time between the Gulf and Japan. Remedies discussed included security alert systems, electric fences around the decks, enhanced naval protection, stricter vetting of crews and port operatives. There is little enthusiasm for ships to carry weapons and grenades.

Threats to ports x Ship used as a bomb in a port city/area (e.g. Boston or Tokyo Bay) x Inadequate Energy-Related facilities at Ports. x Threats posed by lack of thorough inspection at international ports (2% shipping freight is checked)

Threats to pipelines: an Iraqi case study This session relied on up-to-the-minute reports by security forces and a leading private security company in Iraq. Iraq’s main 669KM oil artery, the North/South pipeline is more or less out of action in the North on account of sabotage. The bulk of Iraqi oil exports now run southwards through the area under British protection: Internal resistance is driven by a complex variety of political and personal motives. There is a general resentment of foreign occupation and an awareness of the risks of power shifts through the period of transition. From outside, resistance is reinforced by radicals pouring into Iraq, many with al-Qaida support. Urban unrest re lack of electricity, water, security etc is rising.

8

Tribal unrest on tribal boundaries is endemic. Threats to security are becoming more diverse and complex. Without any control or customs inspection on the Iraqi borders, al-Qaida has almost 100% freedom of movement. Remedies include establishing tight control of the borders, introducing more trunk-road checks, extension of the “cash-for-arms” scheme and the building up of a network of new medical centres and hospitals, all of which provide a stream of valuable local intelligence. The security of the pipelines has been largely handed over to contracted Iraqi companies who complain that the State must be active in supervising overall responsibility, which is currently lacking.

Conclusion The two discernible Middle East flashpoints in the year ahead are Iraq and Saudi Arabia. There are high hopes of normalisation of relations with Iran and Libya. Palestine remains a pan-Arab rallying cry. Oil market leadership is entering a process of change. In the longer-term, acute competition for Gulf oil and gas exports looks extremely likely and will present the lead-consumer governments with new and difficult challenges.

STRATEGIC ACTIONABLE NET-CENTRIC BIOLOGICAL DEFENSE SYSTEM S. Kornguth Director, Countermeasures to Biological and Chemical Threats Institute for Advanced Technology, University of Texas at Austin, USA

Abstract:

1.

Technologies required for strategic actionable net-centric biological defense systems consist of : 1) multiplexed multi-array sensors for threat agents and for signatures of the host response to infection; 2) novel vaccines and restricted access antivirals/bacterials to reduce emergence of drug resistant strains pre- and post-event; 3) telemedicine capabilities to deliver post-event care to 20,000 victims of a biological strike; and 4) communication systems with intelligent software for resource allocation and redundant pathways that survive catastrophic attack. The integrated system must detect all threat agents with minimal false positive/negative events, a seamless integrated broad-band communications capability that enables conversion of data to actionable information, and novel pre- and post-event treatments. The development of multiplexed multi-array sensors, appropriate vaccines and antibiotics, and integrated communication capabilities are critical to sustaining normal health, commerce, and international activities.

INTRODUCTION

The overarching objectives in developing effective countermeasures to biological threats are to protect the Defense community and citizenry from such threats, and to develop agile responses to unanticipated events considering that successful terrorists do the unexpected. The need for protection against and responses to biological threats has been strikingly demonstrated by the use of anthrax contaminated letters that were sent through the U.S. mail in October 2001. That attack resulted in human illness, the loss of life, and discontinuity of government operations because of contamination of federal office buildings in Washington, DC. A recent report prepared by the Center for Strategic and International Studies (CSIS) and supported by the Defense Threat Reduction Agency (DTRA) of the 17 D. Morrison et al. (eds.), Defense against Bioterror: Detection Technologies, Implementation Strategies and Commercial Opportunities, 17–27. © 2005 Springer. Printed in the Netherlands.

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Department of Defense (DoD) came to the conclusion that the U.S. is at present not well prepared for a similar attack using anthrax1. The major problems include a lack of: 1) a clear chain of command, and 2) tools to provide the public with information that permits appropriate responses. The incidence of Congo-Crimean hemorrhagic fever in Afghanistan, an area where coalition forces are being deployed, increases this need. The potential threat posed by emergent disease (e.g., Severe Acute Respiratory Syndrome [SARS] and West Nile Fever virus) or from a major release of a contagious biological agent such as smallpox, has been a growing concern at all levels of the international community. This article outlines and discusses a new strategy that is needed if we are to be fully capable of sensing, preventing, and managing biological threats.

2.

NEW PARADIGM

The current paradigm addresses biological and chemical terrorist threats in a vertical (stove-piped) response. In the arena of developing sensors for the detection of biological agents, the paradigm has been to develop separate detectors for each agent or to develop a platform for detecting 12-24 threat agents using a single probe for each agent. There is a lack of an interactive networked communication system that is capable of managing a devastating emergent disease. To establish a highly networked system that is rapid enough to permit effective protection, it is necessary to evolve from the stove-piped, compartmentalized model currently in use to an integrated, fused, probabilistic, and frequently updated information model. Multiplexed multi-array sensor systems, capable of recognizing all bacterial or viral genomic materials related to pathogenicity or of recognizing antigenic domains that are specific indicators of pathogens are one component of a network needed for rapid detection and identification of biological threats. With respect to therapeutics, modern technologies for vaccine and antibiotic production provide decided advantages over older methods. The traditional vaccines require extensive development times before they become available for human use and undesired side effects commonly result from vaccines produced by these protocols. The cost associated with developing and testing vaccines, using traditional technology, approximates 50-100 million dollars per vaccine. The dissemination of antibiotics and antivirals through the world markets has resulted in the appearance of pathogenic bacteria and viruses that are resistant to these drugs. One approach to reduce the development of antibiotic resistance is to restrict the distribution of newly developed antibiotics. Such an approach presents ethical and social dilemmas. The consideration of options available for reduction of drug

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resistance, prior to a threat event, may permit development of a rational policy. A major problem facing our nations in the event of a biological attack or emergent disease is the large numbers of patients that can be anticipated to require medical treatment. Although improvements in emergency medical care and hospital equipment have been achieved during the past two decades, the ability of any community to manage an outbreak of infectious disease affecting >10,000 people is lacking. Rapid progress has been achieved whereby medical care can be provided to patients at sites that are distant from primary caregivers using telecommunication systems (e.g., the Armed Services in theater, large scale HMO providers such as Kaiser Permanente, or the correctional institutions in the U.S.). The funds needed to acquire telecommunication equipment for such distributed medical care delivery are estimated to be less than 100 million dollars for the entire U.S. At the present time such a distributed care system is not readily available. The new paradigm couples a network centric integrated sensor alert system that can detect all threat agents simultaneously, with a seamlessly integrated communication software capability that converts large scale data to actionable information. For this to be effective, the sensor system must yield minimal false positive and false negative results. The new paradigm incorporates large-scale databases on normative values of threat agents in many regions of the world so that significant changes in real time can be detected. The paradigm also includes the development and implementation of novel pre- and post-event treatment capabilities. Attention must be paid to the ability of high level decision makers and operators to recognize that a new state of threat has emerged, based upon output of the sensors, data fusion system, and iconographic display. Ambiguity of data, lack of an autonomous processing system, and high stress on the operator (e.g., sleep deprivation, lack of training) may all compromise the utility of a highly networked system of systems. What is needed for this new paradigm to succeed? The needs include multiplexed multi-array sensors for biological agents that infect people, livestock, and edible crops. The agents of concern include many on the Militarily Critical Technologies List prepared for the Office of the Secretary of Defense. We need multiplexed multi-array sensor systems with high specificity and selectivity for the rapid detection of host responses to infection. We need a new generation of effective therapeutics, including vaccines, antibiotics, and antivirals. A network centric intelligent communication system that can provide accurate comprehensible information to decision makers (from command officers to unit operators) is required. To minimize morbidity and mortality and optimize containment of disease, a biosurveillance system based on archival health databases, statistical models, and data mining strategies that can provide an early alert to a disease outbreak is required.

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In many cases the operator may be required to understand the meaning of acquired data in very short time periods (seconds to minutes) if the response is anticipated to change the outcome of an engagement. The Tactical Decision Making Under Stress (TADMUS) program is one example of such a situation. In the biological threat arena, the detection and identification of toxins require rapid analysis and operator comprehension. The large increase in numbers of sensors (for high explosives [HX], biological and chemical agents, meteorological conditions) together with the rapid changes in op tempo required to manage emergence of clinical disease would suggest a need for the development of systems capable of autonomous generation of an alert when threat conditions arise.

3.

CURRENT STATE OF TECHNOLOGY NEEDED FOR THE NEW PARADIGM

In the sensors area, the genomes of most biological threat agents have been sequenced and the signatures of toxins described. Novel multiplexed multi-array sensor-platform systems utilize the genomic datasets to detect the appearance of threat levels of these agents. In the therapeutics area, researchers are working towards identifying critical antigenic epitopes of these agents. New therapeutics can emerge that have an antigen binding capacity significantly greater than antigen-cell receptor binding, resulting in the potential for agent neutralization. Technologies have been developed over the past decade for the development of new drugs and DNA based vaccines. Restricted access antivirals/antibacterials will need to be developed to reduce the emergence of drug resistant strains pre- and post-event. A significant development in our program at The University of Texas at Austin (UT-Austin)2 has been the novel design and production of an antibody that binds the anthrax PA antigen 1000 times stronger (Kd<10-11) than any antibody to date. The antibodies were produced using phage display technology for selection of the antibodies. In tests with experimental rodents in a controlled facility, administering the Bacillus anthracis PA antigen to the animals resulted in 100 percent fatalities, whereas the co-administration of the newly developed antibody against the PA antigen resulted in 100 percent survival2. Research is also being conducted to determine unique nucleic acid sequences in the genome of pathogenic bacteria and viruses that contribute to the pathogenic properties of the organisms. This information is being used to develop multiplexed assay systems that can detect selected agents simultaneously. By quickly screening for multiple pathogenicity island sequences or pathogenic factors, end-users will have the capability to detect the first signs of emergent disease without requiring screening for

STRATEGIC NET-CENTRIC BIOLOGICAL DEFENSE SYSTEM

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each particular organism. In the communications area, researchers are developing ‘belief maintenance’ software to provide decision makers some estimate of the validity of incoming data. An estimate of information credibility is critical to effective decision-making in crisis situations when one must rely on an 80 percent solution (i.e., 80 percent of needed information is available). Waiting for a 100 percent solution could have a catastrophic impact on response effectiveness. In the area of telecommunications, researchers are developing the means to provide effective medical triage to victims in a contaminated hot zone. The hot zone in this case refers to a region experiencing an outbreak of a highly contagious disease that causes death in a significant percentage of infected individuals. Advanced telecommunications technology can permit physicians and other medical experts at remote locations to provide medical information and support care delivery to personnel in the hot zone. Prior training of these personnel (from physicians to local citizens) is required. An extensive use of local persons will be necessary if it is deemed inadvisable to introduce health care workers and communications experts into the hot zone; the external support teams are required to provide ‘back-fill’ support to the overburdened local community. Biosurveillance systems are being developed to serve as an early warning of emergent disease. A variety of databases are being developed that are health related. Examples of these databases include school absenteeism, over-the counter drug sales, hospital emergency clinic visits, and archival records on the incidence of diseases in different geographic regions, CONUS and OCONUS. Each database must be statistically characterized regarding parameters such as variance, confidence intervals, seasonality, etcetera, and be integrated into validated predictive models. Once the reference databases are in place and suitably modeled, statistically significant departures from baseline values can be detected and transmitted in real time to decision makers through intelligent communication systems.

3.1

Technology Gaps

A number of critical technology gaps exist that must be addressed if we are to recognize, prevent, and minimize the effect of biological agents. These gaps include: deficiencies in the availability of multiplexed multi-array agent sensors and platforms; critical reagents; capability for large-scale production of effective vaccines, antibiotics and antivirals; ability to treat a large number (10,000) of infected people 24/7 for several weeks in a biological hot zone; archival biosurveillance databases and intelligent and secure communications networks. With the new capabilities and devices anticipated during the next decade, approaches that address these gaps include the use of

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autonomous (e.g., cell phone-based) microelectronic detectors for the transmission of data on agent exposure, development of novel antibodies, antibiotics and antivirals to manage disease outbreaks, and establishment of global surveillance systems for emergent diseases (e.g., SARS, West Nile Fever, Congo-Crimean Hemorrhagic Fever).

3.2

Research Areas

Because of the broad scope of needs for technology to prevent and minimize biological threats, a number of research areas have been identified as critical. These include: the scientific validation that a biological incident has occurred (requisite tools/capabilities include situation awareness systems, sensors and signatures); the availability of medical countermeasures (vaccines, pharmaceuticals, and medical transport); and a highly effective communications network for the secure transmission of data and the conversion of such data to comprehensible information so that decision makers can take appropriate actions.

3.3

Sensors Research

For effective sensors, a variety of materials are being developed that include effective high-affinity binders of biological threat agents. The high affinity binders include antibodies, cDNA gene probes, polynucleotide aptamers, and combinatorial chemicals. Using phage display methods, antibody fragments can be selected that have a high affinity for agents such as anthrax toxin and brucella. Another binding system that has been examined uses polynucleotide aptamers about 31 nucleotides long that have good binding affinity to ricin toxin. These sensor materials require opto/electronic transduction platforms. Sensor platform research currently is being focused on micro-electro-mechanical systems (MEMS) devices, microelectronics technology, microfluidics (laboratory-on-a-chip), DNA/protein microarrays, and transduction devices. Efforts are also being directed toward the development of multiplexed multi-array systems that detect approximately 100 biological threat agents of concern. For military application, it is essential that sensor systems can detect and identify agents present in samples rapidly, using platforms that are small and have low power requirements.

3.4

Therapeutics Research

With current approaches, the development-to-market of new vaccines, antibiotics, and antivirals is in the order of 5-10 years. A paradigm shift to

STRATEGIC NET-CENTRIC BIOLOGICAL DEFENSE SYSTEM

23

newer culture and DNA-based technology is needed if we are to have an effective response to a major biological or chemical event. Current estimates regarding the time required for developing and fielding new vaccines and antibiotics/antivirals to specific threat agents, using new technology and expedited approval, is in the order of three years.

3.5

Communications Research

While current computer/informatics research includes the development of telecommunications assets, a critical need in the communications area is the development of seamless integrated communication networks. These network centric systems enable the conversion of data to actionable information. Research is being conducted to provide intelligent agent software designs for such communication systems. This will enable an enhanced accuracy in critical decision-making and resource allocations. The integrated system must have redundant pathways that can survive a catastrophic attack. The communication system must be capable of integrating data on an emerging threat in a timely manner, and provide useful information for public safety coordination and perimeter management.

3.6

Telemedicine Needs

Telemedicine capabilities can aid in the delivery of post-event care to 10,000-20,000 victims of a biological strike in a densely populated area for 24 hours a day, seven days a week, for several months. In the event of smallpox attack in which 10,000 people develop clinical symptoms of infection within 7-10 days following exposure, local hospitals and medical response capabilities would be overwhelmed if current treatment protocols were used. Telemedicine allows physicians at a remote location from the hot zone to provide medical support via telemedicine capabilities (visual, audio) to aid local physicians in treating patients. A treatment level of 50 patients per day per physician would require 200 physicians to provide telemedicine care for 10,000 patients. Each physician would require telemedicine devices; hence 200 telemedicine devices would be required at the remote location, and a similar number in the hot zone. A national telemedicine system could include the establishment of approximately eight telemedicine response centers nationally, interconnected via satellite to telepresence and telemedicine/robotic systems. The remote care capability reduces the likelihood of the dissemination of disease to physicians and communities in which the physicians reside. A telemedicine system would also retain health care delivery in communities providing health care back-fill.

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3.7

STRATEGIC NET-CENTRIC BIOLOGICAL DEFENSE SYSTEM

Networked Operations at the Coordinating Level and Lower Echelons of Command

A decision making component is required for coordinating the delivery of actionable information. Figure 1 illustrates such a flow chart. In threat situations, data developed from sensor arrays, surveillance systems, and therapeutics inventories can be electronically encrypted and transmitted via intelligent communication networks to decision makers for appropriate actions. The decision makers include individuals, government authority, medical care experts (doctors, hospitals, the Centers for Disease Control and Prevention [CDC], etc.), and the military.

3.8 1. 2. 3. 4.

Network Centric Response to Threat Data Fusion and Human

Perception/Comprehension Primary issue of concern Full situation awareness is contingent on at least four elements including: Large scale acquisition of data (i.e., SIGINT, MASINT, HUMINT, sensors) 5. High fidelity communication of data sets to autonomous processing centers 6. Data fusion involving weighting of data and marked reduction in data volume to yield information that provides users a common operational picture 7. Rapid comprehension of time dependent information by operators facilitated by new iconographic displays, training, measures of vigilance

STRATEGIC NET-CENTRIC BIOLOGICAL DEFENSE SYSTEM

25

Figure 1.

3.9

Proposed Goal of the Autonomous Data Processing

The end goal is achievement of a rapid appropriate action in response to detection of threat (within minutes of threat identification). In order to meet this time constraint in a real world scenario, it is probable that the man-inthe-loop may have a denial capability rather than an approval function.

3.10

A Strategy to achieve this Goal

The tools required for autonomous weighting of data and subsequent reduction of data elements for particular missions remain to be developed and agreed upon. The technologies required for data acquisition, communication, and autonomous processing fundamentally differ from that required for comprehension by an operator. The three technologies are systems that must be developed prior to deployment and will have known probabilities of accuracy and reliability. The fourth element involves the training and state of vigilance/alertness of the operator as well as the development of software (e.g., icons, data mining, and compression) used to display threat conditions. The point of the fourth element is to permit an operator to have rapid comprehension of the state of threat in a rapidly changing environment. Because there is a time factor involved in the comprehension of threat conditions by an operator, and in the translation of the information into action, the fourth element must include temporal qualities. Since the time dependence (seconds to minutes) of an intense

STRATEGIC NET-CENTRIC BIOLOGICAL DEFENSE SYSTEM

26

threat situation will differ from that involved in a peacekeeping or supply distribution situation (many minutes to hours on the average), the autonomous weighting factors and data reduction factors can be expected to vary widely. This variability complicates programming of autonomous systems.

3.11

Basic Principles of Human Decision Making Under Stress

Command teams on the modern information-age medical delivery front face an increasing variety of cognitive stressors: information ambiguity, information overload, fatigue, and fear of contagion and quarantine. There is a requirement for a useful, predictive model of the effect of these stressors on individual and collective cognition within the medical delivery team. A model to quantify stress experienced by the caregiver and to identify countermeasures and mitigators of stress, develop organizational strategies for optimum performance under stress is needed. Psychological assessments that can predict individual and team cognitive functioning and physiological markers that can determine quantitatively and objectively the effect of stress experienced on an operators vigilance have been identified (Table 1). The identification of specific physiological markers that are predictive of stressinduced changes in complex cognitive functioning will aid in the construction of autonomous weighting systems. Table 1. Stressors and Measures Stressors Measurement Information Technologies Ambiguity Cognition +++ Behavioral + Markers Emotional +++ Assessment † Observer/Control +++ ler Ratings Auditory/Visual Evoked Potential (P300, P600) Respiration / Ventilation Rate Cardiac q-t Interbeat Interval

Information Overload +++ +

Fatigue

Social Isolation

Danger

++ +

++ +

++ ++

+++

+++

++

+++

+++

+++

++

++

+++

+++

+++

+

++

++

++

+

+++

+++

+++

+++

++

+++

+++

+ Degree of reactivity to measurement † (e.g., Voice Stress Analysis)

STRATEGIC NET-CENTRIC BIOLOGICAL DEFENSE SYSTEM

4.

27

ACKNOWLEDGEMENTS

The research reported in this document was performed in connection with Contract number DAAD13-02-C-0079 with the U.S. Edgewood Chemical Biological Command.

REFERENCES 1.

2.

Lessons from the Anthrax Attacks: Implications for U.S. Bioterrorism Preparedness. CSIS Funded by the Defense Threat Reduction Agency of the Department of Defense. David Heyman investigator. March 2004. Maynard, J.A., Maassen, C.B.M., Leppla, S.H., Brasky, K., Patterson, J.L., Iverson, B.L., and Georgiou, G., "Protection against Anthrax Toxin by Recombinant Antibody Fragments Correlates with Antigen Affinity," Nature Biotechnology, vol. 20, pp. 597-601, June 2002.

Chapter 2 TOXIC CHEMICALS AND RADIOACTIVE SUBSTANCES AS REASON OF OCCURRENCE OF ACUTE POISONING IN UKRAINE Sergey Ryzhenko Dnepropetrovsk Region Sanitary-Epidemiological Station. 39a. Philisofskaja St., Dnepropetrovsk 49000, Ukraine

The chemical terrorism is a new threat to mankind safety, vastly exceeding in scale the results of the most modern firearms and representing one of the cheapest forms of terrorism. The first information about "terrorism" dates from 431-404 years B.C., when ammonium smoke was used in the course of the Peloponness wars. In 1899 as a result of the International Peace Conference Agreement in Hague the use of artillery projectiles equipped with poisoning gas was prohibited. However it is in the XX century during World War I - in 1915 that the first large-scale use of poisonous material occurred on the battle site near the city of Ypres, Belgium. During World War I were applied more than 100 000 tons of toxic chemicals, as a result of which perished 90 000 soldiers and more than a million were affected. In 1925 in Geneva a protocol was signed, which forbade the use of bacteriological and chemical weapons, however this was not sufficient for the countries to stop further production, use and accumulation of chemical weapons. In 1972 several countries signed in Geneva a Convention on biological and toxin weapons and undertook the obligation to continue the negotiations for an agreement to forbid chemical weapons also. In 1992 the participants of the Geneva negotiations agreed on a text of the Convention on prohibiting the development, production, accumulation and use of chemical weapons and on their destruction. In 1993 the Convention on chemical weapons was open for signing. During the ceremony for the Convention signing in January in Paris, 130 countries supported the agreement and international disarmament with their signatures. In February of the same year in Hague was founded a Starting-up commission with the task to prepare the coming into effect of the Convention. In spite of these efforts, in 1995 in Japan the “Aum Sinrike” sect made the terrorist act in Tokyo underground by using the chemical weapon sarin. Beside the 5000 affected, 12 persons perished. 13 C. Dishovsky et al. (eds.), Medical Treatment of Intoxications and Decontamination of Chemical Agents in the Area of Terrorist Attack, 13–19. © 2006 Springer. Printed in the Netherlands.

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Toxic Chemicals and Radioactive Substances

Only in 1997 the Convention on chemical weapons took effect for 87 member-countries – initiators of the Convention. According to the Convention to perform the requirements was created the Organization for Prohibition of Chemical Weapons (OPCW) with headquarters in Hague. The Convention on Chemical Weapons is an international agreement, which forbids the use of chemical weapons and aims at liquidating the chemical weapons for ever and all over the world. The Convention provides the basis for supervision by the Organization for Prohibition of Chemical Weapons and for destruction of the available spare chemical weapons, as well as objects, which are used for production of chemical weapons, and for checking industrial objects for prevention not to allow the production of new chemical weapons. The Organization for Prohibition of Chemical Weapons also assists the international cooperation and exchange by research information so that people and governments use chemical investigations for peace purposes. Modern highly toxic chemicals and biological agents could fall into terrorist hands through various channels: - appropriation of military storehouses and arsenal, where chemical weapons are kept; - appropriation of enterprises equipped with facilities for chemical protection; - supplies from production, storage and trade companies; - illegal production in underground laboratories. - for the last 10-20 years there has been a qualitative growth in production of synthetic preparations for treatment of the various diseases, possessing a broad spectrum of pharmacological influence. Some psycho-pharmacological drugs can be used by terrorists for solving their own problems. The sanitary and epidemiological service in Dnepropetrovsk area has functions, which have been entrusted by the legislation of Ukraine thus contributing to the preventive safeguarding of the people from poisoning by toxic chemicals applicable in industry and agriculture. For the industrial areas of Dnepropetrovsk the problem for protection from industrial wastes from enterprises is traditionally actual. At present over 8,2 billion tons of industrial wastes to miscellaneous degrees of toxicity are stored in this area. The wastes from the chemical production occupy more than 6,2 km2. On the territory of the enterprise there continue to be accumulated wastes from the galvanic technology of 1st and 2nd degree of danger. The big worries remain the petroleum production waste, whose amount sharply increased in connection to the stormy development of the town public transport. A requirement was introduced in this respect to undertake expert sanitary-hygienic measures for the treatment of wastes in accordance to article 24 of Law on Wastes of Ukraine, № 187-98-VR from 05.03.98 and articles 25 and 33 of Law of Ukraine "On the provision of sanitary and epidemic welfare for the population". Annually the sanitary and epidemiological service conducts over 500 expert operations. Till

Sergey Ryzhenko

15

01.01.2005 the sanitary-hygienic expert operations connected with wastes covered over 90% of the enterprises. For the expert operations with wastes we used the official report form III for toxic wastes, issued by order of the Ministry of statistics of Ukraine on 23.07.93 under № 162. According to this form subject to accounting are all types of toxic wastes, including production unfit for recycled use and containing dangerous elements. In order to elaborate a state system for registration of wastes, with Resolution 1360 from 31.08.98 the Council of Ministers of Ukraine approved the order for registration of sites where wastes are produced, recycled and used. With order № 41 from 17.02.99 the Ministry for environmental protection of Ukraine approved a form for register cards. At present such register cards should be agreed on by the organs of state control of the district. The evaluation of the register cards is made on the basis of a sanitary-hygienic expertise of the wastes treatment. Special attention is paid to specified as being of high degree of danger wastes and their chemical composition in the register cards. When making an expert evaluation, specialists at the sanitary and epidemiological service should take into account two types of waste storage sites: temporary and for a longer period of time. Temporary storage sites at the territory of the enterprise are given permission only by way of exception. Longer storage sites concern such installations as midding slime and slag collectors, mouldboards etc. Supervision of the sanitary and epidemiological service in this case is directed mainly to technical equipment requirements of the storage site and conducting selective laboratory monitoring of the atmospheric air, ground and water composition in the area of the wastes storage. Annually the district uses hundreds of the tons of different pesticides (more than 100 different names) in agriculture. According to the Ukrainian sanitary regulation for transport and preservation of chemical preparations for plant protection, this activity can be performed only by transport vehicles and storehouses, which possess sanitary passports for ecological safety, issued by the State sanitary and epidemiological service and the Inspection for ecological safety. To work with pesticides are allowed only persons that have passed physical examination and have the corresponding education together with the special permit. The rather thoughtless use of chemical compounds for plant protection in the second half of the XX century has brought about the accumulation in the storehouses of some facilities of about 1000 tons of preparations that are unfit for use, forbidden or unidentified. The sanitary and epidemiological service jointly with the Ecological inspection and the District station for plant protection are conducting an inventory of the storage sites of these toxic wastes. Inventory data with indications for the place of the storage, the names of the preparations and their quantity is kept in a computer database. Funds have been assigned in the regional and local budgets for improving the storing of these toxic material, according to information from

16

Toxic Chemicals and Radioactive Substances

the sanitary-and-epidemiological service and the ecological inspection. So in 2004, about 150 tons of unfit and unidentified pesticides were recycled and stored according to regulations. The same is planned for 2005, but these actions do not solve the problem as a whole. Unfortunately, the district is unable for the moment to use or destroy this dangerous toxic material. The optimum solution for this issue would be the storage or destruction by such entities that have the respective licenses for performing this kind of work. The district will benefit the most from a method for destruction of this toxic material called "Mobile plasma complex for recycling of unfit and unidentified pesticides", which has been designed by the "Colorit" Institute of Dnepropetrovsk. However the mentioned method still has to be ecologically and sanitary-epidemiologically evaluated by experts. A system of laboratory monitoring has been organized in the district which controls indications for pesticides and other chemical substances in objects of the environment, raw material supplies and food products. The status of the atmospheric air and the water basins especially the water collectors and recreation sites is systematically checked for contents of toxic material. Food products are systematically checked for safety indicators, including pesticides contents and chemical compounds. For this procedure highly sensitive GC and HPLC methods are used. But a number of problems exist. Currently to our regret, the laboratories of the state sanitary and epidemiological service lack modern indication instruments and express methods equipment, allowing a quick determination of the presence of toxic material. With the development of chemical industry the moment has come to equip the laboratories of the sanitary and epidemiological services with modern instrumentarium and methods, capable quickly to establish small (insignificant) quantities of the different groups of poisoning material in the air, the water and the food products. An issue with equal significance for the Dnepropetrovsk district is the provision of radiological safety for the population. The sanitary and epidemiological service of the Dnepropetrovsk district also provides supervision for the observance of radiological safety rates during operation of ionizing radiation sources in public health, industry and other industrial branches. It carries out studies on food products, drinking water, construction material, gamma-survey of the territory. Under special supervision is the 30 km zone of the Zaporozhsk NPS (nuclear power station). Annually the radiological subdivisions of the sanitary and epidemiological service of Dnepropetrovsk district are conducting measurements for over 1000 different tests and for more than 2000

Sergey Ryzhenko

17

measurements of the power of the external gamma radiation dose on different objects and in open air. Measurements of the dose load of about 500 individuals chosen amonprofessionals and random population, living in the 30 km zone are executed annually. Our specialists execute works on determining the affiliation of suspicious objects to the ionizing radiation source, on estimating the degree of danger, as well as organization of actions for its neutralization. Radiological damages connected with loss, finding and appropriation of radioactive sources are not something unusual for the district. In 1999 such events have gained mass character in the Dnepropetrovsk district. As a rule such sources are used in different branches of production in radio-isotope instruments for the technological control of different processes. The sources "are packed" in special leaden blocks, which provide the required level of protection from the harmful effect of the ionizing radiation for the person. Considering the potential danger of the irradiation, the specialists of the sanitary and epidemio-logical service request higher caution from the workers providing the safety of these instruments. However from 1999 till our days, a series of ravishment of ionizing radiation sources occurred on the territory of the district, and in the first place in the town of Krivoi Rog. From 1994 to 1998 only three such incidents were registered in the district, while in 1999 - five, three of which were connected to ravishment. It should be noted that all the stolen sources were of radionuclides caesium - 137. The results of the analysis made by the sanitary and epidemiological service of the city of Krivoi Rog, revealed that the main reason that provoked the cases of ravishment was the formal attitude of the responsible persons towards their duties, for which they were punished in accordance with the sanitary legislation. Fallen in the hands of criminals, which as a rule have a very remote notion on the danger of ionizing radiation, radioactive sources become a serious threat for the life and health of the terrorists themselves, as well as of casual persons. And the attempt to extract the ampoule with the radioactive source from its protection block is equal to expose oneself to radiation. Besides, in the event of destruction of the ampoule containing radioactive material, radioactive contamination of a large territory can occur. Such an incident happened already in Taromskoe suburb of Dnepropetrovsk. Unpleasant”findings” often occur. Thus, in August 1999 during sorting scraps of the ferrous metal production of the ZAO "Ygprom" factory in the city of Krivoi Rog, a suspicious object was discovered labelled "Danger.Radioactivity". Further the object was identified as being a radioisotope instrument for monitoring the degree of freezing of air-planes. During the last years ionizing radiation radionuclide sources were repeatedly withdrawn from illegal circulation in Dnepropetrovsk,

18

Toxic Chemicals and Radioactive Substances

Pavlograde, Dnepropetrovsk district, a small towns Carichanka and Megevaia. In 2000 the law-enforcement organs arrested an inhabitant of small towns Carichanka when he was trying to sell a defensive block with a radionuclide source. After that, his house was inspected thoroughly and three similar blocks were discovered hidden at different places. In September 2001 a citizen of Kiev was arrested in a suburb of Dnepropetrovsk, who was also trying to sell a defensive block with ionizing radiation source previously stolen in Doneck district. After a year practically the same situation was repeated in Pavlograde city. There a Russian citizen tried to sell on the territory of Ukraine a radioactive source bought on the black market. In the course of the investigations it was discovered that the radioactive source was stolen from one of the enterprises in the Chelyabinsk district. In all operations of the law-enforcement organs against illegal handling of the ionizing radiation sources, active participation took the specialists of the Dnepropetrovsk sanitary and epidemiological station. Anxious to avoid possible income of nuclear waste with the scrap metal, the large metallurgical enterprises began introducing different systems for input radiation supervision. The most efficient from a number of operating systems is the automated "Cordon" in Krivoi rog metallurgical factory. Due to its installation, for a period from 2001 till now, it was not permitted for the smelting to be polluted by more than a group of ten radiation polluted batches. Amongst the radioactive waste most varied objects were discovered among which different nodes and spare parts polluted with caesium-37 from Chernobil, as well as natural radionuclide radium -226. There can be found radionuclide instruments also. For the last 5 years under our participation 22 radiological incidents were liquidated. According to our counts we took part in five successful joint operations against illegal possession of ionizing radiation sources with the law-enforcement organs. An orderly system for interaction of the authorities on all levels including lifeguards, ecological, sanitary and epidemiological service, specialized from the radiological protection organizations was created in the Dnepropetrovsk district in order to counteract with a well-timed reaction to any information about suspicious for radiation objects. As a result of the coordinated activities of all interested services, now it takes less than one day from the incoming of the information on suspicious radiation object till its neutralization. The facts about finding powder of unknown origin in postal envelopes shocked the world. In 2003-2004 on the basis of laboratory analysis for extremely dangerous infections, the regional sanitary and epidemiological station specialists investigated more than 44 mailings, containing unknown powdery material. Fortunately, according to the laboratory analysis, results in all the cases were negative.

Sergey Ryzhenko

19

In the majority of the countries, the necessary equipment and potential have been provided for to counteract the main affections from chemical incidents. These measures include not only the setting up of specialized organizations and institutions such as public health establishments or emergency committees and commissions, but also creation of reliable information sites and systems. More efforts for the protection of the population from all types of terrorism are needed based on the already available systems and initiatives.

1

AN OVERVIEW

Sir David Gore-Booth KCMG KCVO Workshop Co-Director Chairman, Windsor Energy Group, Former Ambassador to Saudi Arabia, Middle East Director, Foreign & Commonwealth Office, UK

The principal event of 2003 was the US/UK invasion of Iraq. I was the only person in 2003 here at the Windsor Energy Group who said that there would not be an invasion (mainly because I could not understand the rationale for it and did not want to be thought to support it even by default). I still believe it was a mistake to invade and, although not sorry to see the back of Saddam, I believe this misadventure will cause more problems than it solves: it has had no beneficial affect on the oil market (on the contrary the price remains very high – not least since US reserves are at their lowest level for 29 years). The invasion of Iraq has had no beneficial effect on the Middle East Peace Process. The effect, in my view, has been quite the opposite: Sharon seems more sceptical than ever about the road map and is under no real pressure from the US Similarly, the war has had no clear beneficial effect on “good governance” in the Middle East: even Thomas Friedman now accepts it will take Israeli withdrawal from the Occupied Territories to “strip the worst Arab leaders of an excuse not to reform”. In terms of the War on Terror, the invasion of Iraq has turned the country from a peripheral into a central front and it has diverted attention from the War on Terror’s main target, Osama Bin Laden. If anyone should have been discovered in a rat hole it was him! And through all this Afghanistan remains a worry. On a different note, increased security has become an obsession in the US, even at the cost of civil rights. We see concrete evidence of this

11 H. McPherson et al. (eds.), Emerging Threats to Energy Security and Stability, 11–12. © 2005 Springer. Printed in the Netherlands.

12

manifested in new political phenomena in the US such as the Patriot Act legislation and the construction of prison complex in Guantanamo Bay. International organisations such as the UN, NATO and the WTO are in a state of confusion while the EU remains under real strain over the drawing up of the new constitution, its stability pact and the steady appreciation in value of the Euro. Corporate governance is in difficulty whether in Russia (Yukos), Italy (Parmalat) or UK (Shell) and the problem is ongoing in the US. There are, however, some reasons to be cheerful. Both India and Pakistan have little relevance to central energy issues, a successful rapprochement will increase both country's demands for energy. The region will become a large energy-consumer alongside China, whose economic growth is already boosting demand, still leading in consumption. Libya and Iran’s entry back into the Global community is due as much to painstaking European diplomacy as it is to knee-jerk US unilateralism. In all, I foresee another very stressful year ahead with the approach of the US election prompting more government by gut and gimmick than by good sense.

NATURAL TOXINS: THE PAST AND THE PRESENT E. Grishin Deputy Director of Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry, Russian Academy of Sciences, ul. Miklukho-Maklaya, 16/10, Moscow 117997, Russia

Abstract:

1.

Different bacteria, viruses and toxins constitute a potential menace for people. The number of toxins that could be applied for a bioterrorist attack with real public health risk, though, is relatively limited. However, these natural toxins could cause difficult troubles. The objective of this paper is focused on the toxins of various origins that might be used as a biological weapon. To be used in such a way the toxin should be highly lethal and easily produced in large quantities. Our current knowledge on natural toxins is conducive to select the toxin list threatening public health. At present this list includes a few bacterial and plant toxins, as well as a set of toxins produced by algae and molds. Novel methods of toxin detection should be able to monitor the presence of many toxins at the same time.

INTRODUCTION

Natural toxins vary widely in animal, plant and microbial organisms. Over the past decade we can witness the remarkable progress in our knowledge about chemical nature of toxin molecules and their biological action. In fact the natural toxins represent an immense number of various compounds that causes injury, illness or death of a living organism. Unfortunately today we are a witness to bioterrorism. Bioterrorism is the intentional use of biological agents to cause illness of people. Some of the natural toxins can be used as potential biological weapons. The basic knowledge and biological weapon expertise are very needed to select a set of natural toxins that could be utilized for bioterrorism. Civilian population should be informed about the potential biological weapons of bioterrorism. The number of toxins that could be applied for a bioterrorist attack with real public health risk is relatively limited. However, these natural toxins could 29 D. Morrison et al. (eds.), Defense against Bioterror: Detection Technologies, Implementation Strategies and Commercial Opportunities, 29–45. © 2005 Springer. Printed in the Netherlands.

30

NATURAL TOXINS: THE PAST AND THE PRESENT

cause difficult troubles. Regular national or international meetings are devoted to toxin research. The balance between openness and biosecurity is still under discussion. The use of biological weapony has been known for centuries, culminating in special research programs run by several countries. The objective of this paper is focused on the toxins of various origins that might be used as biological weapons. Our current knowledge on natural toxins is conducive to select the toxin list threatening public health. At present this list includes a few bacterial and plant toxins, as well as a set of toxins produced by algae and molds, and some animal toxins. To be included in this list the toxin should fit some criterions. There are at least four such criterions: availability and simplicity of manufacture, simplicity of application, efficacy of action (toxicity) and reasonable stability.

2.

BIOLOGICAL ACTIVITY OF NATURAL TOXINS

Poisonous organisms have been known for centuries. Many scientists have been involved in the investigation of toxic molecules from these organisms. Their attention has been directed on identification, isolation, structure determination, biological and toxicological studies of toxic molecules which constitute a great many of natural toxins. Natural toxins can generally be divided into several broad groups according to their origin or their chemical nature or their biological activity. When the potential weapons for bioterrorism are reviewed for needed characteristics the biological activity/toxicity attracts special attention. A number of selected toxins and their toxicity are presented in Table 1. Natural toxins listed in the Table 1 possess a wide range of toxic activity with LD50 value for 10-5 mkg/kg up to 200 mkg/kg. Potential agent for bioterror should be highly lethal and easily produced in large quantities. Only botulinum toxin and ricin meet these requirements. Some other natural toxins as saxitoxins, microcystins and mycotoxins could be included in the list of potential biological agents for bioterror.

NATURAL TOXINS: THE PAST AND THE PRESENT

31

Table 1. Toxicity of some natural toxins.

Name Botulinus Tetanus Abrin (ricin) Palytoxin Taipoxin Cobrotoxin Scorpion toxin Batrachotoxin Tetrodotoxin Curare Potassium cyanide

3.

LD50 (mkg/kg) -5 1.1x10 -5 2.8x10 2.7 0.15 2.0 75 9.0 2.0 8.0 200 1000

Mr 150 000 140 000 65 000 3 300 42 000 7 819 7 249 538 319 696 65

LD50 (mol/kg) -16 0,6x10 -16 2.0x10 -11 4.3x10 -11 4.5x10 -11 4.8x10 -9 9.6x10 9 1.2x10-9 3.7x10 -9 25x10 -8 29x10 -4 1.5x10

BOTULINUS

Botulinum toxin (BTX) is the most potent biological toxin yet known [1]. BTX is a protein complex consisting of 150 kDa di-chainal toxins referred as botulinum neurotoxins associated with non-toxic companion proteins. It is produced by Clostridium botulinium, C. baratii, and C. butyricum, anaerobic, spore forming gram-positive bacteria, which are the causative agents of botulism. Respiratory failure secondary to paralysis of the respiratory muscles during botulism development can lead to death. BTX acts preferentially on peripheral cholinergic nerve endings to block acetylcholine release. Due to the severity and potency of this neurotoxin, its importance as a biological weapon is of major concern to public health officials [2]. The ability of BTX to produce its effects is largely dependent on its ability to penetrate cellular and intracellular membranes. Thus, toxin that is ingested or inhaled can bind to epithelial cells and be transported to the general circulation. BTX is structurally organized into three domains endowed with distinct functions (Fig.1): high affinity binding to neurons, membrane translocation and specific cleavage of proteins controlling exocytosis of neurotransmitter [3, 4]. Toxin that reaches peripheral nerve endings binds to specific receptors on the cell surface, which may comprise

32

NATURAL TOXINS: THE PAST AND THE PRESENT

gangliosides. The binding mediated by the toxins heavy chain is followed by endocytotic internalization of neurotoxin/receptor complex. Thus, it penetrates the plasma membrane and the endosome membrane upon acidification of vesicles, when the light chain of the neurotoxin is translocated into the cytosol. Here, the light chain (Zn2+-endopeptidase) cleaves one or two among three synaptic proteins (VAMP-synaptobrevin, SNAP 25, and syntaxin) (Fig.2). All three protein targets of BTX play a major role in the fusion of synaptic vesicles at the release sites. Subsequently, their cleavage is followed by blockage of neurotransmitter exocytosis.

Figure 1. Schematic structure of Botulinum toxin.

Type A BTX is the most widely used in human drug trials [5]. It has become the treatment of choice for blepharospasm, hemifacial spasm, cervical and laryngeal dystonia. It may also be used in the treatment of patients with oromandibular dystonia and limb dystonia, and has been used successfully in the treatment of spasticity and cerebral paralysis. The toxin also alleviates pain and may be used in therapeutic trials for prediction of the response to surgical elongation.

NATURAL TOXINS: THE PAST AND THE PRESENT

33

Figure 2. Cleavage of synaptic proteins (VAMP, SNAP 25 and syntaxin) by the light chain of Botulinum toxin.

4.

RICIN

Ricin is a naturally occurring toxin derived from the beans of ubiquitous worldwide castor oil plant Ricinus communis [6, 7]. Taking into account the volume of annual castor beans processing in the world and fairly easily production of the toxin from the waste mash with an output reaching 5% ricin by weight, the toxin should be considered as being potentially widely available. The ready availability of ricin, coupled to its extreme potency, has identified this protein toxin as a potential biological warfare agent. Therapeutically, its cytotoxicity has encouraged the use of ricin in “magic bullets” to specifically target and destroy cancer cells, and the unusual intracellular trafficking properties of ricin potentially permit its development as a vaccine vector. The most hazardous routes of ricin exposure are with inhalation and injection. It is quite stable and extremely toxic. The lethal dose by inhalation (breathing in solid or liquid particles) and injection (into muscle or vein) has been estimated, approximately 5-10 mkg/kg, that is 350-700 mkg for a 70 kg adult. Ricin intoxication can manifest as gastrointestinal hemorrhage after ingestion, severe muscle necrosis after intramuscular injection, and acute pulmonary disease after inhalation. Death had ensued within hours of deliberate subcutaneous injection.

34

NATURAL TOXINS: THE PAST AND THE PRESENT

Figure 3. Schematic structure of ricin

Ricin is a heterodimeric protein made up of two hemagglutinins and two toxins being able to fatally disrupt protein synthesis by attacking the ribosome [8-10]. The X-ray structure of ricin has been elucidated. The toxins consist of two polypeptide chains (A and B chains), which are joined by a disulfide bridge (Fig. 3). The A chain is a specific N-glycosidase with a prominent active site cleft. The B chain is a two domain lectin. To enter the cytosol and reach its target, the toxin must cross an internal membrane and avoid complete degradation without compromising its activity in any way [11, 12]. Cell entry by ricin involves a series of steps: 1) binding, via the ricin B chain, to cell surface glycolipids or glycoproteins having beta-1,4-linked galactose residues; 2) uptake into the cell by endocytosis; 3) entry of the toxin into early endosomes; 4) transfer, by vesicular transport,of ricin from early endosomes to the trans-Golgi network; 5) retrograde vesicular transport through the Golgi complex to reach the endoplasmic reticulum; 6) entry of the A chain in the cytosol, 7) interaction of A chain with the ribosome to catalyse the depurination reaction (Fig. 4). It has been reported that even a single molecule of ricin reaching the cytosol can cause the cell death. Combining our understanding of the ricin structure with ways to cripple its unwanted properties will also be crucial in the development of a long awaited protective vaccine against this toxin.

NATURAL TOXINS: THE PAST AND THE PRESENT

35

Figure 4. Some stages of ricin action: binding to cell membrane, endocytosis, transport to Goldgi apparatus and the ER, translocation of A subunit to the cytosol.

5.

SAXITOXINS

Paralytic shellfish poisoning is caused by a group of toxins produced by both marine and freshwater algae. Marine dinoflagellates Alexandrium catenella, A. minutum, A. ostenfeldii, A. tamarense, Gymnodinium catenatum and Pyrodinium bahamense produce saxitoxins. In freshwater, blue-green algae, namely Anabaena circinalis, also manufacture the toxins. At the time of algal blooms (red tides), shellfish accumulate saxitoxins leading to paralytic shellfish poisoning (PSP) which, in extreme cases, causes death due to respiratory paralysis. People walking near the surfline during red tide events often complain of sore throats and difficulty breathing. This is as a result of inhaling a toxin-laden aerosol generated by the pounding surf. A debate continues about whether bacteria produce saxitoxin, or influence dinoflagellate production of the toxins [13]. There are about 20 derivatives of saxitoxin responsible for paralytic shellfish poisonings. Saxitoxin was named after the butter clam Saxidomonus giganteus, from which it was first isolated in 1957 [14]. The chemical structure of saxitoxin was determined in 1975 [15]. The toxin is a tricyclic molecule containing two guanidino groups (Fig 5). The polar nature of saxitoxin allows it to readily dissolve in water and lower alcohols being insoluble in organic solvents. Chemically, saxitoxin is very stable although it can be inactivated by treatment with strong alkali. It can be kept in dilute acidic solutions for years without loss of its activity. Saxitoxin itself is highly toxic. It is toxic by ingestion and by inhalation, with inhalation leading to rapid respiratory collapse and death.

36

NATURAL TOXINS: THE PAST AND THE PRESENT

Figure 5; Chemical structure of saxitotin (STX) and five saxitoxin derivatives.

Saxitoxin exerts it’s toxic effect by interfering with the transmission of signals through the nervous system. The toxin binds specifically to the voltage-gated sodium ion channels and prevents their normal function. This blocks the creation of a proper action potential and the nerve cell no longer has the means to transmit a signal. Saxitoxin blocks the sodium channel selectively without any effect on other types of ion channels. The toxin binds to a site on the external surface of the sodium channel. Owing to the potent and specific sodium channel blocking action, saxitoxin has become a useful tool in neuroscience research in various studies of ion channels [16].

6.

BLUE GREEN ALGAE TOXINS (CYANOBACTERIA TOXINS)

Cyanobacterial toxins or cyanotoxins are produced by fresh- and seawater photosynthetic prokaryotes (blue-green algae) of cosmopolitan occurrence [17-19]. When environmental conditions are suitable for their growth, cyanobacteria may proliferate and form toxic blooms in the upper, sunlit layers. The occurrence of cyanobacteria and their toxins in water bodies used for the production of drinking water poses a technical challenge for water utility managers. The cyanotoxins differ from the intermediates and cofactor compounds that are essential for cell structural synthesis and energy transduction. They present acute and chronic hazards to human and animal health and are responsible for or implicated in animal poisoning, human gastroenteritis, dermal contact irritations and primary liver cancer in humans. These low molecular weight toxins (microcystins, nodularins,

NATURAL TOXINS: THE PAST AND THE PRESENT

37

saxitoxins, anatoxin-a, anatoxin-a(S), cylindrospermopsin) are structurally diverse and their effects range from liver damage, including liver cancer to skin irritation and neurotoxicity. There are indications of the accumulation of cyanobacterial toxins in fish, and crop plants and they are also associated with the deaths of human dialysis patients.

6.1

Microcystins

Microcystins are a family of more than 50 structurally similar monocyclic heptapeptide hepatotoxins produced by species of freshwater cyanobacteria, primarily Microcystis aeruginosa. They are characterized by some invariant amino acids, including one of unusual structure, which is essential for expression of toxicity (Fig. 6) [20]. Microcystins are chemically stable, but suffer biodegradation in reservoir waters.

Figure 6: Chemical structure of Microcystins

The most common member of the family is microcystin. It has an LD50 in mice and rats of 36-122 mkg/kg by various routes, including aerosol inhalation [21]. Acute liver hemorrhage and death occur with high doses of microcystin, which is also a potent tumor promoter. Although human illnesses attributed to microcystins include gastroenteritis and allergic reactions, the primary target of the toxin is the liver, where disruption of the cytoskeleton, consequent on inhibition of protein phosphatases, causes massive hepatic hemorrhage. Uptake of microcystins into the liver occurs via a carrier-mediated transport system, and several inhibitors of uptake can antagonise the toxic effects of microcystins. Microcystins are very strong protein phosphatase inhibitors, which are needed for regulation

NATURAL TOXINS: THE PAST AND THE PRESENT

38

of structural proteins of the cell [22, 23]. They covalently bind the serine/threonine protein phosphatases 1 and 2A (PP1 and PP2A), thereby influencing regulation of cellular protein phosphorylation.

6.2

Anatoxins

Anatoxins are a group of low molecular weight neurotoxic alkaloids produced by different species of fresh-water cyanobacteria (Anabaena flosaquae, Anabaena planktonia, Oscillatoria, Aphanizomenon), in isolation or in combination with hepatotoxins [24]. Not all strains of the causative species are toxic and there are no systemic indications to the presence or absence of anatoxin in a particular strain. Three common anatoxins have been described: anatoxin-a and homoanatoxin-a are secondary amines and anatoxin-a(S) is a phosphate ester of a cyclic N-hydroxyguanine structure (Fig. 7) Anatoxin-a and homoanatoxin-a are neurotoxic alkaloids, the main effect of which is production of a sustained postsynaptic depolarizing neuromuscular blockade causing respiratory arrest [25]. The toxin binds strongly to the nicotinic acetylcholine receptor [26]. It mimics acetylcholine action and is thus able to open the ion channel. However, the toxin cannot be deactivated by acetylcholineesterase which force the ion channel to be open. Anatoxin-a and homoanatoxin-a are potent neurotoxins causing rapid death in mammals (LD50 in mice of approx. 250 mkg/kg) [27]

Figure7: Chemical structures of anatoxins.

Anatoxin-a(S), the second type of anatoxins, is the only natural organophosphate known. It is more water-soluble than synthetic organophosphates. Anatoxin-a(S) is more potent towards mice (LD50 in mice is approximately of 50 mkg/kg) [28]. It binds to acetylcholineesterase and acts as its inhibitor [29], thereby causing toxicity through the exhaustion of muscle cells. However the toxin is unable to cross the blood-brain barrier to influence brain cholinesterase activity. In addition to respiratory difficulty,

NATURAL TOXINS: THE PAST AND THE PRESENT

39

anatoxin-a(S) unlike anatoxin-a, induces hypersalivation in mammals as well as other symptoms more typical of neurotoxicity such as diarrhea, tremors and nasal mucus discharge.

7.

MYCOTOXINS

Mycotoxins are low molecular weight secondary metabolites of mould or fungi [30-32]. These compounds are non-volatile and may be sequestered in spores or secreted into the growth substrate. Numerous but not all fungi species produce mycotoxins with variation of toxin production depending on the substrate. There are over 200 recognized mycotoxins, however, the study of mycotoxins and their health effects on humans are still in the progress. Many mycotoxins are harmful to humans and animals when inhaled, ingested or brought into contact with human skin [33]. Diseases in animals and human beings resulting from the consumption of mycotoxins are called “mycotoxicoses”. The mechanism of micotoxicity involves interference with various aspects of cell metabolism, producing neurotoxic, carcinogenic or teratogenic effects. The toxins vary in specificity and potency for their target cells, cell structures or cell processes by species and strain that produces them. They are nearly all cytotoxic, disrupting various cellular structures such as membranes, and interfering with vital cellular processes such as protein, RNA and DNA synthesis [34]. Most mycotoxins possess immunosuppressant properties that vary according to the compound. The toxicity of certain fungal metabolites such as aflatoxin, ranks them among the most potently toxic, immunosuppressive and carcinogenic substances known [35].

7.1

Aflatoxin

Aflatoxins are a group of closely related mycotoxins that are widely distributed in nature. Aflatoxin is one of the most potent carcinogens known to man and has been linked to a wide variety of human health problems [36]. Aflatoxins B1, B2, G1, and G2 are produced in grains in both field and storage by Aspergillus flavus and A. parasiticus which are common in most soils and are usually involved in decay of plant materials. Aflatoxin persists under extreme environmental conditions and is even relatively heat stable at temperatures above the boiling point of water. Roasting and some microbial treatments may sharply reduce but not eliminate the aflatoxin content. The toxins pose a significant public health concern as diseases resulting from ingestion of aflatoxins, include acute liver disease to cancer development. Mutagenesis by aflatoxins is caused by the reaction of these

40

NATURAL TOXINS: THE PAST AND THE PRESENT

electrophilic chemicals with one of the purine or pyrimidine bases in DNA resulting in irreversible changes in normal cells [37, 38].

Figure 8. Chemical structure of Aflatoxin B1

Aflatoxin B1 (Fig. 8) is the most potent carcinogen known for the liver. It is a specifically metabolized into epoxide form by the action of the mixed function mono-oxygenase enzyme systems (cytochrome P450-dependent) in the tissues (in particular, the liver) of the affected animal [37]. This epoxide is highly reactive and can form derivatives with several cellular macromolecules, including DNA, RNA and protein.

7.2

Ochratoxin

Ochratoxin is primarily produced by Aspergillus ochraceus, Penicillium viridictum, which have been found in some samples of food and feed grains [30, 39].

Figure 9: Chemical structure of Ochratoxin A.

NATURAL TOXINS: THE PAST AND THE PRESENT

41

Ochratoxin is damaging to the kidneys and liver and is also a suspected carcinogen. Ochratoxin is absorbed from the small intestine and, in plasma, binds to serum albumin. The prolonged half-life of the toxin results from its absorption by proximal tubules and enterohepatic circulation. [40]. The chemical structure is composed of an isocumarin part linked to lphenylalanine (Fig. 9). Ochratoxin inhibition of phenylalanine hydroxylase and other enzymes that use phenylalanine as a substrate is based on this structural homology. The inhibition is competitive to phenylalanine resulting in protein synthesis inhibition, and is reversed by an excess of this amino acid. The effect of ochratoxin A on protein synthesis is followed by an inhibition of RNA synthesis, which might affect proteins with a high turnover. Recently, ochratoxin was also found to enhance lipid peroxidation both in vitro and in vivo. This inhibition might have an important effect on cell or mitochondrial membranes and be responsible for the effects on mitochondria that have been shown by several authors [24].

7.3

Trichothecenes, T-2 Toxin

Fusarium tricinctum and some strains of F. graminearurm, F. equiseti, F. sporotrichioides, F. poae, and F. lateritium commonly found in grains, produce T-2 toxin and other toxic trichothecenes [30, 41]. Feed contaminated with these toxins must be handled carefully because these toxins can cause severe skin irritation and bleeding from lungs. Upon ingestion, trichothecenes cause a modulation effect on cell-mediated immunity and alterations in gastrointestinal propulsion, and can produce tremors, incoordination, depression, and headaches [42]. Very little information is available relating to their toxicokinetics and toxicodynamics in humans. As with most other mycotoxins, the only control is to avoid contaminated feeds.

Figure 10. Chemical structure of T-2 toxin

42

NATURAL TOXINS: THE PAST AND THE PRESENT

T-2 toxin (12,13-epoxytrichothecene) is one of the more deadly toxins (Fig. 10). If ingested in sufficient quantity, T-2 toxin can severely damage the entire digestive tract and cause rapid death due to internal haemorrhage. T-2 toxin has been implicated in the human diseases alimentary toxic aleukia and pulmonary hemosiderosis. The toxin mainly affects mitotic cells of the gastrointestinal tract and the lymphoid system and promotes a transient and reversible aberration in a single enzymatic reaction to cell death. Regardless of the end point measured, the toxic response involves the interactions of virtually all-subcellular processes: membrane transport and permeability, chemical metabolism, DNA function, and energy production/expenditure. T2 toxin rapidly crosses the cell membrane of cells and binds to the intracellular targets. It affects the polyribosome structure and thus inhibits protein synthesis being irreversible inhibitor.

8.

BIOTOXIN DETECTOR

Development of fast and sensitive methods for the detection of natural toxins is of great importance because of the threat of bioterrorist attacks. In addition, biotoxin assays are used in food and medical industry and environmental monitoring. At the present time, laboratory methods for the detection of biotoxins involve animal tests, microbiological methods, PCRbased DNA assay, and immunological methods (direct and competitive immunofluorescence methods or ELISA). Immunoassays are the most sensitive, convenient, and least time-consuming and may be used as a method of choice for rapid detection of biotoxins in field conditions. However, these methods do not allow one to carry out simultaneous test for the presence of several toxins. In contrast, microchip based methods allow parallel analysis of different biotoxins. An array biosensor for the simultaneous detection of several toxins has been developed by Ligler et al. [43-44]. In this sensor, biotinylated capture antibodies were immobilized in columns on avidin-coated waveguides on the surface of glass slide. Electronic microchips with capture antibodies were proposed to detect fluorescein-labeled staphylococcal and cholera toxins (direct immunoassay) [45]. Another example of biochips for the assay of pathogenic organisms and their toxins is the technology that uses surfaceenhanced Raman scattering microscopy (SERS) for the detection of the antibody-antigen complexes [46]. Despite good sensitivity and low detection time that are achieved with the mentioned above systems, these biochips are produced by rather sophisticated technologies and/or complex instruments are needed for the detection of signals.

NATURAL TOXINS: THE PAST AND THE PRESENT

43

Microchips on the basis of three-dimensional hydrogels have been developed by Mirzabekov et. al. [47]. Gel microchips with immobilized antibodies were already used for quantitative assay of tumor-associated markers with the sensitivity as low as 0.2 ng/ml.

9.

CONCLUSION

Some natural toxins can be used as agents for bioterrorism, and their potential for future use is a major concern. Although the list of potential agents is rather short some natural toxins should be under special attention. Sensitive methods of toxin detection have to be developed.

REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14.

15. 16. 17. 18.

L.L. Simpson, Identification of the major steps in botulinum toxin action, Annu Rev Pharmacol Toxicol. 44 (2004) 167-193. D. Josko, Botulin toxin: a weapon in terrorism, Clin Lab Sci. 17 (2004) 30-34. G. Lalli et al., The journey of tetanus and botulinum neurotoxins in neurons, Trends Microbiol. 11 (2003) 431-437. B. Poulain and Y. Humeau, Mode of action of botulinum neurotoxin: pathological, cellular and molecular aspect, Ann Readapt Med Phys. 46 (2003) 265-275. C. Singer, Indications and management of botulinum toxin, Rev Neurol. 29 (1999) 157162. S.M. Bradberry et al., Ricin poisoning, Toxicol Rev. 22 (2003) 65-70. M.J. Lord et al., Ricin. Mechanisms of cytotoxicity, Toxicol Rev. 22 (2003) 53-64. J. Robertus, The structure and action of ricin, a cytotoxic N-glycosidase, Semin Cell Biol. 2 (1991) 23-30. J.M. Lord, L.M. Roberts and J.D. Robertus, Ricin: structure, mode of action, and some current applications, FASEB J. 8 (1994) 201-208. S. Olsnes and J.V. Kozlov, Ricin, Toxicon 39 (2001) 1723-1728. K. Sandvig et al., Ricin transport into cells: studies of endocytosis and intracellular transport, Int J Med Microbiol. 290 (2000) 415-420. J. Wesche, Retrograde transport of ricin, Int J Med Microbiol. 291 (2002) 517-521. M.R. Watters, Organic neurotoxins in seafoods, Clin Neurol Neurosurg. 97 (1995) 119124. E.J. Schantz et al., Paralytic shellfish poison. VI. A procedure for the isolation and purification of the poison from toxic clams and mussel tissues, J.Am.Chem.Soc. 79 (1957) 5230-5235. E.J.Schantz et al., The structure of saxitoxin, J.Am.Chem.Soc. 97 (1975) 1238-1239. T. Narahashi, M.L. Roy and K.S. Ginsburg, Recent advances in the study of mechanism of action of marine neurotoxins, Neurotoxicology 15 (1994) 545-554. J.F. Briand et al., Health hazards for terrestrial vertebrates from toxic cyanobacteria in surface water ecosystems, Vet Res. 34 (2003) 361-377. P.V. Rao et al., Toxins and bioactive compounds from cyanobacteria and their implications on human health, J Environ Biol. 23 (2002) 215-224.

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19. G.A. Codd, C.J. Ward and S.G. Bell, Cyanobacterial toxins: occurrence, modes of action, health effects and exposure routes, Arch Toxicol Suppl. 19 (1997) 399-410. 20. R.M. Dawson, The toxicology of microcystins, Toxicon 36 (1998) 953-962. 21. K. Bischoff, The toxicology of microcystin-LR: occurrence, toxicokinetics, toxicodynamics, diagnosis and treatment, Vet Hum Toxicol. 43 (2001) 294-297. 22. B.M. Gulledgea et al., The microcystins and nodularins: cyclic polypeptide inhibitors of PP1 and PP2A, Curr Med Chem. 9 (2002) 1991-2003. 23. M.M. Gehringer, Microcystin-LR and okadaic acid-induced cellular effects: a dualistic response, FEBS Lett. 557 (2004) 1-8. 24. Toxic Cyanobacteria in Water: a guide to their public health consequences, monitoring and management. Chorus, E. & Bartram, J. (Eds.) World Health Organisation 1999, E&FN Spoon London & New York. 25. W.W. Carmichael, D.F. Biggs and P.R. Gorham, Toxicology and pharmacological action of anabaena flos-aquae toxin, Science. 187 (1975) 542-544. 26. C.E. Spivak, B. Witkop and E.X. Albuquerque, Anatoxin-a: a novel, potent agonist at the nicotinic receptor, Mol Pharmacol. 18 (1980) 384-394. 27. N.B. Astrachan, B.G. Archer and D.R. Hilbelink, Evaluation of the subacute toxicity and teratogenicity of anatoxin-a, Toxicon 18 (1980) 684-688. 28. N.A. Mahmood and W.W. Carmichael, The pharmacology of anatoxin-a(s), a neurotoxin produced by the freshwater cyanobacterium Anabaena flos-aquae NRC 525-17, Toxicon 24 (1986) 425-434. 29. N.A. Mahmood and W.W. Carmichael, Anatoxin-a(s), an anticholinesterase from the cyanobacterium Anabaena flos-aquae NRC-525-17, Toxicon 25 (1987) 1221-1227. 30. P.S. Steyn, Mycotoxins, general view, chemistry and structure, Toxicol Lett. 82-83 (1995) 843-851. 31. D. Bhatnagar and K.C. Ehrlich, Toxins of filamentous fungi, Chem Immunol. 81 (2002) 167- 206. 32. J.W. Bennett and M. Klich, Mycotoxins, Clin Microbiol Rev. 16 (2003) 497-516. 33. R. Kappe and D. Rimek, Fungal diseases, Prog Drug Res. Spec No (2003) 13-38. 34. S.E. Browne and M.F. Beal, Toxin-induced mitochondrial dysfunction, Int Rev Neurobiol. 53 (2002) 243-279. 35. R. Goldman and P.G. Shields, Food mutagens, J Nutr. 133 Suppl 3 (2003) 965S-973S. 36. H.N. Mishra and C. Das, A review on biological control and metabolism of aflatoxin, Crit Rev Food Sci Nutr. 43 (2003) 245-264. 37. M. McLean and M.F. Dutton, Cellular interactions and metabolism of aflatoxin: an update, Pharmacol Ther. 65 (1995) 163-192. 38. C.P. Wild and P.C. Turner, The toxicology of aflatoxins as a basis for public health decisions, Mutagenesis. 17 (2002) 471-481. 39. G. Dirheimer and E.E. Creppy, Mechanism of action of ochratoxin A, IARC Sci Publ. 115 (1991) 171-186. 40. V. Berger et al., Interaction of ochratoxin A with human intestinal Caco-2 cells: possible implication of a multidrug resistance-associated protein (MRP2), Toxicol Lett. 140-141 (2003) 465-476. 41. D.L. Sudakin, Trichothecenes in the environment: relevance to human health, Toxicol Lett. 143 (2003) 97-107. 42. P.P. Williams, Effects of T-2 mycotoxin on gastrointestinal tissues: a review of in vivo and in vitro models, Arch Environ Contam Toxicol. 18 (1989) 374-387. 43. J.B. Delehanty and F.S. Ligler, A microarray immunoassay for simultaneous detection of proteins and bacteria, Anal. Chem. 74 (2002) 5681-5687.

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44. F.S. Ligler et al, Array biosensor for detection of toxins, Anal. Bioanal. Chem. 377 (2003) 469-477. 45. K.L. Ewalt et al, Detection of biological toxins on an active electronic microchip, Anal. Biochem. 289 (2001) 162-172. 46. A.E. Grow et al., New biochip technology for label-free detection of pathogens and their toxins, J. Microbiol. Methods 53 (2003) 221-233. 47. A.Yu. Rubina et al., Hydrogel-based protein microchips: manufacturing, properties, and applications, BioTechniques 34 (2003) 1008-1022.

Chapter 3 BIOMONITORING OF EXPOSURE TO CHEMICAL WARFARE AGENTS Noort, D., Van Der Schans, M.J., and Benschop, H.P. Division of Chemical & Biological Protection, TNO Prins Maurits Laboratory, P.O. Box 45, 2280 AA Rijswijk,The Netherlands

Abstract:

An overview is presented of the major methods that are presently available for biomonitoring of exposure to chemical warfare agents, i.e., nerve agents and sulfur mustard. These methods can be applied for a variety of purposes such as diagnosis and dosimetry of exposure of casualties, verification of nonadherence to the Chemical Weapon Convention, health surveillance, assessment of low level exposures (Gulf War Syndrome) and last but not least for forensic purposes in case of terrorist attacks with these agents. This paper will focus on methods that are based on the analysis of long-lived protein adducts of CW agents which are detectable weeks or even months after exposure. Examples of real exposure incidents will be described.

Keyword:

biomonitoring; diagnosis; DNA adducts; immunoassay; mass spectrometry; protein adducts, retrospective detectioin; sulfure mustard

1.

INTRODUCTION

Methods to analyze chemical warfare agents (CWA) and their decomposition products in environmental samples were developed over the last decades (1). In contrast herewith, methods for such analyses in biological samples have only recently become available (2). Retrospective detection of exposure to CWA can be useful for various applications. It can be envisaged that rapid diagnostic methods can play a pivotal role in case of a terrorist attack with CWA. In the same context, confirmation of non-exposure of worried citizens is of utmost importance. Also, such methods can be used for forensic analyses in case of suspected terrorist activities (“chemical fingerprints”). It is self-evident that these methods will also be highly valuable from a military point of view, e.g., to establish firmly to which chemicals casualties have been exposed to, which is a starting point for adequate medical treatment, or for health surveillance of workers in destruction facilities of chemical warfare agents. This 21 C. Dishovsky et al. (eds.), Medical Treatment of Intoxications and Decontamination of Chemical Agents in the Area of Terrorist Attack, 21–26. © 2006 Springer. Printed in the Netherlands.

22

Biomonitoring of Exposure to Chemical Warfare Agents

presentation will focus on a number of specific methods currently available for verification of exposure to the most common CWA, i.e., nerve agents and mustard agents. There are basically four methods to diagnose an exposure to a nerve agent: 1. cholinesterase inhibition measurements 2. analysis of hydrolysis products, e.g., alkyl methylphosphonic acids 3. analysis of generated phosphofluoridates after treatment of blood with fluoride ions (“fluoride reactivation”) 4. mass spectrometric analysis of phosphylated peptides after enzymatic digestion of modified cholinesterase. For mustards, there are three distinct methods to assess an exposure: 1. mass spectrometric analysis of low molecular weight urinary metabolites 2. analysis of DNA adducts by means of mass spectrometric or immunochemical methods. 3. mass spectrometric analysis of protein adducts, e.g., to hemoglobin and albumin. Presently available methods to diagnose and biomonitor exposure to anticholinesterases, e.g., nerve agents, rely mostly on measurement of residual enzyme activity of acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) in blood. More specific methods involve analysis of the intact poison or its degradation products in blood and/or urine. These approaches have serious drawbacks. Measurement of cholinesterase inhibition in blood does not identify the anticholinesterase and does not provide reliable evidence for exposure at inhibition levels less than 20 %. The intact poison and its degradation products can only be measured shortly after exposure. Moreover, the degradation products of pesticides may enter the body as such upon ingestion of food products containing these products. In the case of sulfur mustard, analysis of low molecular weight urinary metabolites suffers from the same drawback as in the case of anticholinesterases, i.e., these products are rapidly excreted and provide therefore limited retrospectivity. Similarly, the in vivo lifetime of DNA adducts of sulfur mustard are less than those of protein adducts due to repair of DNA damage. This paper will focus on methods that are based on the analysis of long-lived protein adducts, i.e., on methods 3 and 4 for nerve agents and on method 3 for mustards.

D. Noort et al.

2.

23

NERVE AGENTS

Analysis of phosphofluoridates generated from phosphylated BuChE In principle, organophosphate-inhibited BuChE in human plasma is a persistent and abundant source for biomonitoring of exposure to organophosphate anticholinesterases. Polhuijs et al. (3) developed a procedure for analysis of phosphylated BuChE in plasma or serum samples, which is based on reactivation of the phosphylated enzyme with fluoride ions: this converts the organophosphate moiety completely into the corresponding phosphofluoridate, which is subsequently isolated and quantitated. As in the case of analysis of hydrolysis products this approach identifies the organophosphate except for its leaving group. Moreover, the extent of the organophosphate poisoning can be determined in this way. Furthermore, based on the minimal concentrations of phosphofluoridate that can be analyzed in blood, it can be calculated that inhibition levels ≥ 0.1% of inactivated BuChE (i.e., trace level exposure) should be quantifiable. Evidently, by analyzing the inhibited enzyme instead of the uninhibited enzyme, inhibitor levels can be measured that are several orders of magnitude lower than those based on residual AChE activity. The method is limited by spontaneous reactivation and ageing (i.e., loss of the alkyl moiety from the alkoxy moiety of the phosphyl group) of the phosphylated enzyme and by the natural life span of the enzyme. Application of this method to serum samples of the victims from the Tokyo subway attack and of the Matsumoto incident yielded sarin concentrations in the range of 0.2-4.1 ng/ml serum. Evidently, these victims had been exposed to an organophosphate with the structure iPrO(CH3)P(O)X, presumably with X = F (sarin). Depending on the structure of the nerve agent, a retrospectivity of 2-8 weeks was observed upon analysis of blood samples from rhesus monkeys which had been challenged with a sign-free dose of the nerve agent (4). Mass spectrometric analysis of phosphylated peptides after enzymatic digestion of modified cholinesterase. Recently, Noort et al developed a procedure that is based on straightforward isolation of adducted BuChE from plasma by means of affinity chromatography with a procainamide column, followed by pepsin digestion and LC/electrospray tandem MS analysis of a specific nonapeptide containing the phosphonylated active site serine-198 residue (5). This method surpasses the limitations of the fluoride-reactivation method, since it can also deal with dealkylated (“aged”) phosphonylated BuChE. The method allowed the positive analysis of several serum samples of Japanese victims of the terrorist attack in the Tokyo subway in 1995. Furthermore, the method could be applied for detection of ChE modifications induced by, e.g., diethyl paraoxon and pyridostigmine bromide, illustrating the broad scope of this approach. This new approach

24

Biomonitoring of Exposure to Chemical Warfare Agents

will also allow biomonitoring/retrospective detection of exposure to several organophosphate pesticides and carbamates in one individual.

3.

SULFUR MUSTARD

Mass spectrometric analysis of protein adducts Sulfur mustard is a strong alkylating agent that reacts readily with nucleophiles under physiological conditions. The reaction products of sulfur mustard with these nucleophiles are all potential biological markers of human poisoning. Metabolites derived from an initial reaction with water and glutathione are excreted in urine (2). Adducts to DNA which may be present in various tissues and blood can conveniently be detected by using an immunochemical assay (6). This section will deal with ad-ducts to hemoglobin and albumin, since it is expected that they are persistent and will allow retrospective detection. Upon incubation of human blood with sulfur mustard, it appears that 20-25% of the dose was covalently bound to hemoglobin. The most abundant adduct was the histidine adduct. In addition, the adducts to cysteine, gluta-mic and aspartic acid and to the N-terminal valine residues were detected (7). As a biological marker of poisoning, N-alkylated N-terminal valine has the advantage that it can be selectively cleaved from haemoglobin by a modified Edman procedure using pentafluorophenyl isothiocyanate as reagent. Analysis of the resultant pentafluorophenyl thiohydantoin, using negative ion GC-MSMS after further derivatisation with heptafluorobutyric anhydride, provided a very sensitive method for the detection of the N-alkylated valine. In vitro exposure of human blood to ≥ 0.1 µM sulfur mustard and in vivo exposure of guinea pigs could be detected employing this method. Moreover, the adduct could be detected in samples from victims of accidental exposure to sulfur mustard and CW casualties (8). Recently, a standard operating procedure (SOP) for determination of the sulfur mustard adduct to the N-terminal valine in hemoglobin was developed (9). By using this SOP, it was found that the Nterminal valine adduct in globin of hairless guinea pigs and marmosets subsequent to i.v. administration of sulfur mustard (0.5 LD50) is persistent for at least 56 and 94 days, respectively. Recently, sulfur mustard has been shown to alkylate a cysteine residue in human serum albumin (10). The site of alkylation was identified in a tryptic digest of albumin from blood exposed to [14C]sulfur mustard. A sensitive method for its analysis was developed based on Pronase digestion of alkylated albumin to the tripeptide S-[2-[(hydroxyethyl)thio]ethyl-Cys-Pro-Phe, and detection using micro-LC-MS-MS. In vitro exposure of human blood to ≥ 10 nM sulfur mustard could be detected employing this method. The analytical procedure was successfully applied to albumin samples from Iranian casualties of the Iraq-Iran war.

D. Noort et al.

4. • • •

25

CONCLUSIONS Adducts with macromolecules such as proteins offer long lived biological markers of exposure, possibly up to several months. Gas or liquid chromatography combined with tandem mass spectro-metry are the methods of choice for unequivocal identification at trace levels. Further improvements in retrospectivity and detection limits will hinge on future enhancements of sensitivity and resolution of electro-spray mass spectrometry instruments and of several hybrid configurations.

ACKNOWLEDGEMENTS

This presentation covers work that was funded by the US Army Medical Research and materiel Command, by the Bundesministrerium der Verteidigung, InSan I 3, Germany, and by the Directorate of Military Medical Service of the Ministry of Defence, The Netherlands.

REFERENCES 1. 2. 3. 4.

5.

6. 7. 8.

Chemical Weapons Convention Chemicals Analysis. Mesilaakso, M. (ed.), John Wiley, New York, 2005 (to be published) Noort, D, Benschop, H.P., and Black, R.M. (2002). Biomonitoring of exposure to chemical warfare agents: a review. Toxicol. Appl. Pharmacol., 184, 116-126. Polhuijs, M., Langenberg, J.P., and Benschop, H.P. (1997). New method for retrospective detection of exposure to organophosphorus anticholinesterases: application to alleged sarin vicitims of Japanese terrorists. Toxicol. Appl. Pharmacol., 146, 156-161. Van der Schans, M.J., Polhuijs, M., Van Dijk, C., Degenhardt, C.E.A.M., Pleijsier, K., Langenberg, J.P., and Benschop, H.P. (2004). Retrospective detection of exposure to nerve agents: analysis of phosphofluoridates originating from fluoride-induced reactivation of phosphylated BuChE. Arch. Toxicol., 78, 508-524. Fidder, A., Hulst, A.G., De Ruiter, R., Van Der Schans, M.J., Benschop, H.P., and Langenberg, J.P., (2002). Retrospective detection of exposure to organophosphorus anticholinesterases: mass spectrometric analysis of phosphylated human butyrylcholinesterase. Chem. Res. Toxicol., 15, 582-590. Van der Schans, G.P., Scheffer, A.G., Mars-Groenendijk, R.H., Fidder, A., Benschop, H.P., and Baan, R.A. (1994). Immunochemical detection of adducts of sulfur mustard to DNA of calf thymus and human white blood cells. Chem. Res. Toxicol., 7, 408-413. Noort, D., Hulst, A.G., Trap, H.C., De Jong, L.P.A., and Benschop, H.P. (1997). Synthesis and mass spectrometric identification of the major amino acid adducts formed between sulphur mustard and haemoglobin in human blood. Arch. Toxicol., 71, 171-178. Benschop, H.P., Van der Schans, G.P., Noort, D., Fidder, A., Mars-Groenendijk, R.H., and De Jong, L.P.A. (1997). Verification of exposure to sulfur mustard in two casualties of the Iran-Iraq conflict. J. Anal. Toxicol., 21, 249-251

26 9.

Biomonitoring of Exposure to Chemical Warfare Agents

Noort, D., Fidder, A., Benschop, H.P., De Jong, L.P.A., and Smith, J.R., (2004). Procedure for monitoring exposure to sulfur mustard based on modified Edman degradation of globin. J Anal. Toxicol., 28, 311-315. 10. Noort, D., Fidder, A., Hulst, A.G., Wooffitt, A.R., Ash, D., and Barr, J.R. (2004). Retrospective detection of exposure to sulfur mustard: improvements on an assay for liquid chromatography-tandem mass spectrometry analysis of albumin-sulfur mustard adducts. J. Anal. Toxicol., 28, 333-338.

2

A POLITICAL PERSPECTIVE

Lord Howell of Guildford Conservative Foreign Affairs spokesman, House of Lords and former Secretary of State for Energy, UK

There can be little doubt that we are entering an age of vastly increased political risk when it comes to the world energy situation, and that this coincides with emerging global patterns for both energy supply and demand. Of course the optimists hope that globalisation will bring a new intensity of international cooperation and partnership in energy-related projects, while the pessimists fear armed clashes, violent struggles for control of energy resources and risks at every turn. The realists will foresee a bit of both. I would like to put these new patterns in some sort of perspective, but before doing so allow me a few observations on the local British scene, which is in some respects a microcosm of the problems and challenges that are faced on a grander scale. The position in the UK is that after a decade of relatively problem-free energy flows there are now major dangers ahead on both the supply side and on the generation and distribution sides. For the UK the situation is about to change radically. We will shortly become again, after many years, a net importer of both oil and natural gas, the latter being supplied by new contracts with Norway, Russia, Algeria and possibly Iran. This takes these aspects of energy supply right back into the heart of international politics in the most sensitive areas on earth. Recently the BBC ran a fictional programme describing how a raid by Chechen terrorists on a Russian gas transmission facility had the knock-on effect of blacking out London, via the closing down of numerous gas-fired 13 H. McPherson et al. (eds.), Emerging Threats to Energy Security and Stability, 13–18. © 2005 Springer. Printed in the Netherlands.

14

electricity-generating stations. The detail may have been fanciful, but the underlying thought – that energy flows are now more interwoven and interlinked than ever before – is correct, and even the politicians, who are notoriously ignorant about the complexities and long-term nature of energy projects, felt moved to ask some anxious questions in Parliament. Meanwhile, here at home in the UK, we have to make crucial new decisions on nuclear power. It is no longer a question of ‘keeping our options open’ on nuclear power generation. Decisions have to be made immediately for a decade’s time. Investment in offshore windfarms cannot conceivably fill the gap which will be left by any nuclear closures, quite aside from the fact that they are about to run into environmental objections almost as fierce as those surrounding the treatment of nuclear waste. Finally, we now have to move towards a new generation of techniques for conservation and low energy consumption. There is much work to be done.

Global Demand There is a staggering contrast here between what the more hopeful and idealistic policy-makers and advisors say about the next 25 years and what the hard facts suggest. This is what you hear the more hopeful policy-makers saying about the next ten to twenty years. Reliance on fossil fuels will reduce, carbon emissions will drop dramatically; demand for alternatives will expand, such as current from wind power, tidal power and solar power, although not from nuclear power. There will be massive conservation as a low energy future develops. Vehicles will use much less gasoline, or dispense with gasoline altogether. Households will adopt small-scale energy sources, oil or gas-fired home boilers will generate their own electricity and feed it back into local grids. The reality, however, looks quite different. The IEA brainstorming paper of February 2003 tells us that world energy demand will grow – by about two thirds between now and 2030. Fossil fuels, far from phasing out, will meet 90 percent of these additional needs. World oil consumption will rise from 77 mb/d to 122 mb/d. Nuclear power will decline (in OECD countries to a minimum with the possible

15

exception of France). US imports will continue to rise for both oil and LNG (note that in 1980 US net crude oil imports of 28 percent were deemed ‘far too high’ – now the figure is 68 percent!). By a clear margin, the biggest driver of demand expansion will be the developing countries. China will lead as energy-thirsty nation. By 2121 China’s share of global GDP, says the World Bank, will have more than doubled, from 3.7 percent to 8 percent. By then the Chinese, who already consume more oil daily than Japan, could be importing 10 mb/d against the current level of 2 mb/d plus. Of the IEA-estimated increase in demand, one third will come from OECD countries and two-thirds will come from the developing world.

Rose-tinted supply estimates Now let’s turn to supply patterns – and once again, the cheerful optimists peddle one picture, while reality dictates another. Here’s the optimists’ rose-tinted picture: The Middle East region will emerge possibly de-nuclearized and de-terrorised and its stability will return. Iraq will see output soar as high as 10 mb/d. Saudi Arabia will follow the path of gradual reform but will remain stable; the Ayatollahs in Tehran will realise the folly of economic isolation and join in new patterns of global responsibility; oil and gas will flow in abundance out of Russia with the oil coming especially from the Caspian Sea basin via pipelines through Georgia and Turkey westwards while the oil will flow eastwards to China and possibly Japan. A big expansion in LNG is also foreseen, so that it becomes, in effect, a globally-traded commodity like oil while its price tracks oil closely. The optimists also plan for cleaner coal technologies with successful carbon capture and of course a big growth in renewable energy, hopefully on or ahead of the EU target for renewables of 10% for 2010. All this will require colossal and sustained investment in energy project infrastructures – that is maintenance and development of oil and gas production, new pipeline networks, modern refinery technologies, new terminals and distribution systems and new storage facilities where appropriate.

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A Risky Reality That is the optimist’s view. Now let us see how this Panglossian picture collides with reality. First, the political risks in the post Cold War e-enabled world are getting larger and starker all the time. The Inforation Technology revolution has empowered systems and networks for handling and trading energy supplies beyond the dreams of thirty years ago. But it has also empowered those with a destructive agenda on the same global scale. Second, on a geographical plane, Iraq may or may not settle down in due course (on the whole I am an optimist on this) but the timescale may be much longer than first hoped and the vulnerability of Iraqi oil continues to be demonstrated. Saudi Arabia could well drift into turbulence as the delicate balance between religious extremists and moderate reformers within is upset by upheaval without (especially in Iraq). Russia is stable now but the roots of political settlement do not run deep (and anyway one believes Russian statistics with caution). In Iran the hardline Ayatollahs are far from defeated and the future there looks very unsettled as well. Meanwhile Nigeria and Venezuela have already demonstrated their political unreliability; Algeria has been under attack and looks worryingly unreliable. Key transit countries like Georgia have also been through paroxysms and their difficulties may not yet be over. Turkey may be prospering and its chances for opening negotiations on EU entry may be improving but there are risks there too as the recent hold-up of shipping in the Bosphorus reminds us. North Sea oil output is now starting to decline sharply. As for nuclear power, it was once seen as the great alternative of the future. It now remains riddled with political difficulties both with regard to location and to the handling of nuclear waste. Moreover, over the whole scene hangs the growing terrorist risk – poised (unless frustrated) to inflict deadly damage on increasingly integrated and complex energy systems. Overall, a conservative estimate is that by 2020 half the world’s oil and gas will come from politically unreliable sources. Furthermore, there are the more ‘normal’ investment risks that come on top of these ubiquitous political uncertainties. The capital requirements for underpinning a secure energy future are enormous even at the calmest of

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times. Certain very specific conditions are required for capital to be raised at all. They include stable Governments and governance, sustained political commitment by the authorities concerned – which may have to stretch over the full lifetime of the project – as well as clear and predictable regulations, minimised corruption, respect for the rules of law, property and contract and freedom to repatriate profits. As energy projects become more interlinked and stretch across national borders it becomes necessary in addition to ensure that the same rules apply both sides of every border and fence. Above all, energy investment demands long life and secure contracts between suppliers and customers. Otherwise, who would want to invest their money? Yet markets see things differently. They want maximum flexibility to chop and change and go for the best price. The differences are exemplified here in the Russia/EU energy dialogue. Russia wants to invest $35bn annually in its oil industry. Who is going to stump up that kind of money without very long-term contracts with Western European markets? Even to recite this list of requirements shows how far most of the energy world is from meeting them, or will be able to meet them in the foreseeable future.

It must never happen Finally, I want to make a general comment about broad global stability, which is the fundamental condition for a safe and secure energy future. We hear a good deal about the USA being ‘the only superpower’ and being the new hegemonic empire-builder. This is a very fashionable view in European circles. I believe it is both dangerous and wrong. It is dangerous because it leads straight not just to frenetic anti-Americanism but to the promotion of Europe as a counter-weight ‘empire’ which is a sure recipe for great power conflict, clashes of interest, rocketing defence-spending and divided counsels in coping with terrorism and fanaticism. It is wrong because the USA is not an imperial power, even if it suits its enemies to depict it as one. Its interest is the interest of all free states, which is live and let live, and it so happens that pluralism, if not some specific democratic model, is the best guarantee that societies will remain free and open participants in the global system. Our combined Western

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world energies should be devoted to enabling every society, from the Asian giants like China and India, to the Arab sheikhdoms, to the smallest Balkan or East European state to move, at their own pace, in that direction. That is not imperialism, it is survivalism. I prefer to see the USA as an ‘umbrella’ state, a larger member of a network in which the individual national interests of all, large and small, are inextricably linked. The same can perhaps be said, or ought to be said, of the European Union institutions which provide collective cover for, but not interference in, the security and trade-prosperity of its numerous member states. For Europe and America to divide and become rival blocs would, in my view, provide a new playground for terror and disruption. It would guarantee that the threats to secure energy supplies, which are already substantial, would become many times more so. I hope it never happens.

BIOLOGICAL WEAPONS INSPECTIONS- THE IRAQ EXPERIENCE

E. B. Myhre Professor, Lund University, Department of Infectious Diseases University Hospital Medical Centre, Lund SE-22185, Sweden

Abstract:

1.

Prior to the 1990 Iraq-Kuwait conflict it was well known that Iraq had developed weapons of mass destruction but the extent of its programs were unclear. After the Iraqi defeat in the ensuing Gulf war 1991 the UN Security Council authorized the creation of UN Special Commission for Iraq (UNSCOM) with the purpose of ridding Iraq permanently of weapons of mass destruction. Several conclusions can be drawn from more than ten years of biological weapons inspections in Iraq. Firstly, UNSCOM managed to get a rather clear picture of the past weapons programs. Secondly, it was not possible for Iraq to restart a substantial program with UNSCOM being present in the country. Thirdly, a full and final and complete account of the weapons program could not be established despite the use of the best intellectual and technical capabilities available at the time.

DEVELOPMENT OF BIOLOGICAL WEAPONS

Development and production of biological weapons of mass destruction is an illegitimate activity. In the era of globalization such weapons could end up in the hands of terrorist groups. The dissemination of weapon technology through migration of scientists is another concern. Insight into and control of state-sponsored weapons programs is highly relevant with regards to prevention of international terrorism. Prior to the 1990 Iraq-Kuwait conflict it was well known that Iraq had developed weapons of mass destruction but the extent of its programs were 47 D. Morrison et al. (eds.), Defense against Bioterror: Detection Technologies, Implementation Strategies and Commercial Opportunities, 47–50. © 2005 Springer. Printed in the Netherlands.

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BIOLOGICAL WEAPONS INSPECTIONS- THE IRAQ EXPERIENCE

unclear. After the Iraqi defeat in the ensuing Gulf war 1991 the UN Security Council authorized the creation of UN Special Commission for Iraq (UNSCOM) with the purpose of ridding Iraq permanently of weapons of mass destruction. It was expected to be a quick and easy task. Iraq was supposed to produce a full final declaration of their weapons programs, to hand over remaining weapons and to destroy them under supervision. Instead of full open cooperation Iraq engaged in a policy of concealment and deception. Friendly walk-through inspections were soon transformed into unannounced intrusive on-site visits. Instead of being provided with requested information international UNSCOM experts had to collect the information themselves. This resulted in an atmosphere of mutual distrust. Soon these inspections became high profile activities, closely watched by the mass media and wrongly portrayed as the hunt for weapons of mass destruction. The objectives were to fully understand the Iraqi weapons programs, to map all its components and to ensure that the weapons program was not restarted. In 1999 UNSCOM was transformed in into a new organisation, the UN Monitoring, Verification and Inspections Commission for Iraq (UNMOVIC). Facing the same restraints and an unchanged Iraqi attitude UNMOVIC would not be more successful than UNSCOM in providing a full final and complete account of the Iraq’s programs of weapons of mass destruction. Shortly before the Second Gulf War in 2003 UNMOVIC withdrew its staff from Iraq and the inspection work came to an end. Initially Iraq vehemently denied the existence of any offensive biological weapons program. But 1995 became a turning point with the defection to Jordan of Kamal Hussein, Saddam Hussein’s son-in-law. Kamal Hussein had first class insight into the weapons programs and UNSCOM was immediately notified about the existence of an inconspicuous farm house outside Baghdad. When UNSCOM searched the farm house cases of documents were found revealing among other things an offensive biological research program and a secret production facility. This facility had been visited by UNSCOM expert teams several times but samples collected had failed to detect any biological agents. The Iraqis had successfully sanitized the facility. Yet the location, the construction of the buildings as well as the equipment found there had always roused suspicion. UNSCOM on-site inspections were highly sophisticated information gathering operations. The work was carefully planed and organized by the permanent staff at UNSCOM headquarter in New York City but provision was made for local initiatives for quick responses. Operational plans were often kept secret even from some UNSCOM staff members in order to prevent unwanted dissemination of information. Sites were visited without prior notice yet UNSCOM teams were always accompanied by Iraqi

BIOLOGICAL WEAPONS INSPECTIONS- THE IRAQ EXPERIENCE

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minders. With access to their own helicopters UNSCOM staff members could quickly reach any part of Iraq. Vast amounts of data were accumulated in a highly systematic way. Detailed information had been collected on institutions of interest, their technical equipment and their human resources. The capability of various sites to engage in research and production of biological weapons was critically evaluated. Iraqi minders were always present during site visits including interview sessions with the Iraqi scientists, administrators and laboratory workers. At times the minders could be disruptive and the situation could become ugly. Iraqi government officials normally videotaped entire inspections, a procedure which was very stressful both to the inspectors and the Iraqi who were working at the site. The minders were apparently instructed to assess the area of competence of each new UNSCOM inspector. Occasionally the minders tried to hinder inspections by simply outnumber the UNSCOM team. UNSCOM own linguists were extremely useful on site as their presence made studies of various Arabic documents possible.Dual-use equipment provided a special analytical problem. Such equipment were tagged and only allowed to be moved after prior notice. There were many constraints, some of which were of critical importance. Access to all locations, for example, was one. Presidential palaces, mosques, private homes and facilities used by various security organizations were all off limits. Another constraint was the issue of timing. Inspections were never carried out during the night. The Iraqis could move and hide equipment during the night if they wanted. There was evidence of such activities. UNSCOM withdrew twice from Iraq as the US retaliated with cruise missile strikes for Iraq’s failure to cooperate with UNSCOM. A revisit to a site after an attack was suggested that the Iraqi had known exactly which sites were to be attacked. The Iraqis allowed their staff to take home items of special importance. Items too heavy to be transported to private homes were stored in a caravan some hundred meters away from the buildings as the Iraqis knew from past experience that this was the safest place. Unparalleled experience in conducting weapons inspections was gained from 10 years of work in Iraq. Even with access to the best intellectual capabilities and technical equipment UNSCOM/UNMOVIC could not confirm nor deny that Iraq had retained weapons of mass destruction and had restarted its offensive weapons programmes. Both the intelligence and the scientific community were equally divided on these issues. Different governments made different conclusions based on how they interpreted available data. There were worries that Iraq would restart their program once the sanctions were lifted and UNSCOM gone. We knew that the Iraqi Government kept the weapons groups intact for years. The Iraqi scientists who had been involved in the past program showed no regret. An ongoing

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compartmentalized activity possibly under the auspices of security agencies was also suspected as were transmigration of scientists and movements of equipment to other countries. As soon as the hostilities had ended the Iraqi Survey Group stared to search for proscribed weapons and illegitimate weapons activities. In October 2003, the Iraqi Survey Group presented to the Congress in an interim report that no weapons of mass destruction had been found so far. What was the actual situation in Iraq at the onset of the last Gulf War 2003? Many questions remain unanswered. Did Iraq still possess weapons of mass destruction? Had Iraq restarted its biological weapons program? The answer today is that we still do not know and we might never know.

2.

CONCLUSION

Several conclusions can been draw from more ten years of biological weapons inspections in Iraq. Firstly, UNSCOM managed to get a rather clear picture of the past weapons programs. Secondly, it was not possible for Iraq to restart a substantial program with UNSCOM being present in the country. Thirdly, a full and final and complete account of the weapons program could not be established despite the use of the best intellectual and technical capabilities available at the time.

Chapter 4 NON-RULED MARKET ECONOMY AS A SOURCE OF CHEMICAL TERRORISM. AUTOMOTIVE FUEL: QUALITY AND ENVIRONMENTAL SAFETY William Zadorsky Ukrainian State Chemical-Technology University 8. Gagarin Ave., Dnepropetrovsk 49005 Ukrain

Abstract:

The problems of the market economy influencing the state of environment in Ukraine are illustrated by the example of the Pri-dneprovie region. New examples resul, when ecologically dangerous enterprises and technologies are created in flagrant contradiction with the conception of sustainable development in order to please the requirements of the market in the region. Ecologically dangerous projects are realized, which on the basis of their effects can be named chemical terrorism without overstatement. Special attention was paid to the use in Ukraine of the "special" fuel on the base of wastes of coke factories of Ukraine, containing a carcinogen and benzenel in quantities, which exceed by orders of magnitude the doses accepted in other Europian countries and the rest of the world. Possibilities to decline the harmful influence of such fuel on the population of Ukraine in the market conditions are shown.

Keywords: chemical terrorism; cleaner production; fuel; liquid waste; market economy; rocket utilization; sustainable development

1.

DISCUSSION

At long last, it was announced that, "based on the major ideas and principles declared at the Rio de Janeiro Conference of 1992, Ukraine deems desirable a shift to sustainable development that would ensure a balanced solution to social and economic tasks and to problems of leaving the environment and the potential of natural resources in good order for the current and future generations." 27 C. Dishovsky et al. (eds.), Medical Treatment of Intoxications and Decontamination of Chemical Agents in the Area of Terrorist Attack, 27–48. © 2006 Springer. Printed in the Netherlands.

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Non-ruled Market Economy as a Source of Chemical Terrorism

As is well known, the concept of sustainable development includes three aspects, namely environmental, economic and social. Underestimating any of these facets will lead to a distortion in this equilateral triangle and to a deviation from the overall strategy of sustainability. This strategy can only be implemented when the three tasks are fulfilled simultaneously. The systems approach reveals strong interactions between the three factors of sustainable development. The sustainability will therefore be determined mainly by those parameters that affect at least two of the three factors. The National Academy of Sciences of Ukraine suggested that an economic-environmental-social model be devised and employed for the purposes of the country’s sustainable development. This is a very complex and time-consuming approach that may not be usable at this time of industrial restructuring, privatization and other involved processes occurring in a collapsed national economy. An alternative tactics is put forward, which is applicable at both national and regional level. Instead of mathematical modeling and optimization, it uses systems approach and decision theory techniques. The environmental pollution in Ukraine has reached critical levels. Vehicles, power plants, steel mills and nonferrous metallurgy works are the major air polluters. Pesticides are responsible for much of the harm done to human health. Water pollution continues on a large scale. The Dnieper region is the worst affected among its counterparts in Ukraine. Here, the situation is disastrous because of a combination of energy-intensive industries, thermal power generation, and intensive agriculture, further aggravated by Chernobyl. There is an urgent need to find feasible ways that would stop the ensuing depopulation in Ukraine, such ways to ensure survival that would work before the sustainable development concept has been implemented. In these times of a deep economic crisis, the economic and environment-related issues must be attacked simultaneously, in line with one strategy for a cleaner economy. This would be a change from a policy of anthropogenic impact assessment to that of at-source abatement of pollution. Such a program must be specific, realistic and not contradicting the idea of sustainability. It might be a program of cleaner industrial and agricultural production incorporating a systems principle of ascension from cleaner local units, mills, factories, and areas to a cleaner Ukraine to cleaner multinational regions. What makes our approach rather different from the mainstream international cleaner production (CP) movement is the desire to abolish the dominating "black-box" techniques. Instead of regarding a production facility as no more than a given set of benign inputs and polluting outputs, we insist that one should seek the best ways to affect a prospective cleaner object within the "black box".

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As the major principle of cleaner economy, the systems approach is taken that deals with perfecting any nature-technology system at the various hierarchic levels, from environmental pollution sources to consumers, and takes into account the interactions and mutual effects of all important components. This type of analysis will reveal relationships between the ways to improve processes and the challenges of risk management and nature conservation. The main task is therefore to harmonize the nature-technology relation and, ideally, to engineer high-performance systems featuring desired environmental characteristics at each hierarchic level, so that the favorable environmental background is not impaired and, where possible, even restored. Following are the basic assumptions underlying the cleaner economy concept for Ukraine: At this time of a deep economic crisis, the economic and • environmental challenges must be met simultaneously, in keeping with one strategy of cleaner economy. A move towards a cleaner economy must focus not on consumption, • but rather on perfecting those entities that are actual or potential polluters. • The success of a cleaner economy policy will be largely determined by the availability of professionals well trained in the theory and practice of "economy clean-up" and environmental management. • No cleaner economy will be possible without creating a civilized environmental market. These strategic principles determine some tactical measures for pursuing them. Such measures are applicable to any industry and include: • no waste due to improved selectivity, • neutralizing wastes directly at the origin, rather than at the exit, flexible technologies, • • recycling materials and energy, • conservation of resources, • waste treatment, etc. These tactics must be combined with certain design and process engineering techniques, such as • providing a considerable excess of the least hazardous agent, • minimizing dwell times, • recirculation of materials and energy via closed loops, • concurrent reactions and product separation, • introduction of heterogeneous systems, adaptive processes and apparatuses, • • increasing throughputs, • multifunctional environmental facilities, etc. For a cleaner economy to be affordable an environmental market must be established and market mechanisms set to motion between all its interacting operators. Integration is necessary that would link researchers and developers of environmentally high technologies to designers of equipment to manufacturers to users. Professionals must be trained and

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Non-ruled Market Economy as a Source of Chemical Terrorism

further educated in the fields of industrial ecology and environmental management. Qualified consulting and assessing bodies are needed that would be capable of certifying environmental products, properly performing scientific, engineering and legal assessment, and winning public trust at the environmental market. Legislation is necessary that would give incentives to managers and entrepreneurs promoting cleaner production, ensure benefits to companies upgrading their production facilities to make them more environment-friendly, and stimulate development of an environmental market focused on high technologies, equipment, labor and services and having all proper attributes like competition, arbitration courts, commercial practices etc. The latter paragraph is closely related to the idea of restructuring in the area of material production to be based on developing a socially oriented market economy that would guarantee • a proper life standard for the population, • cleaner production, minimizing environmental loads, material conservation, adoption of new types of activity grounded on environmentally safe technologies, making a more balanced economy by shifting from production of • means of production to consumer goods, and • environmental impact assessment and auditing for all economic projects. The macroeconomic transformations rely on changes in the structure of production and consumption, mainly in industry. This necessitates: • a more pronounced social orientation of industry to increase the relative importance of light and food-processing industries, • an effective combination of industry branches keeping abreast of international requirements and meeting domestic needs, setting limits to raw material and semi-finished product industries, • • stepwise reduction of exports from primary and other material- and energy-intensive industries, • increasing outputs of high-added-value products to facilitate effective utilization of domestic resources, and restructuring the production environment via introduction of recent • scientific accomplishments, conservation of energy and other resources, implementation of waste-free and environment-friendly technologies, application of optimized power sources, waste treatment and utilization. These points are common to the Draft Concept and to the cleaner production concept. How could all that be funded? It would be ridiculous to suggest that comprehensive actions towards a cleaner economy might be supported by the miserable national budget. There is even less reason to believe that any down-to-earth effort to upgrade some specific facility and implement advanced technologies and state-of-the-art equipment might be funded from it. Furthermore, we can hardly rely on the assistance from the

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West, and nobody here believes in assistance not backed by economic interest. What is to be done to make cleaner production profitable, as is the case in the West? One source might be those fines that are imposed on violators of environmental laws in Ukraine. However, no mechanisms of channeling this money to environmental investments are available so far. All over the world, the environmental market is replacing punitive methods of environmental management and those environment protection agencies that are not capable of coordinating and managing cleaner economy projects. Worldwide, the taxation and payments for resources and emissions are devised in such a manner as to make it more profitable for the manufacturer to resolve the environmental issues in-plant, rather than to shift them off to the consumer area. A combination of sanctions with economic incentives for a cleaner production will make the latter not a recipient from, but rather a donor to the government budget.Yet even domination of a cleaner economy policy will not soon guarantee survival of the population under a deep economic crisis like the current one. The anthropogenic damage already caused to nature may prove too heavy and not lending itself to repair within the life span of one or even more generations. An analysis of the man-production-environment system reveals that for survival of human beings the CP concept must be complemented by two more lines of action, namely • adaptation of human body to life in adverse conditions, and • utilization of life support systems. The former approach implies development and implementation of biomedical and unconventional methods for prevention of ailments, adaptation and rehabilitation based on recent scientific findings and combined efforts of scientists, engineers, educators and managers under a degrading environment in Ukraine. These are the major lines to be pursued: setting up a tailored system of environmental education and training • for the population in environmentally damaged areas, relying on the existing environmental education network and the media, • research and development of adaptation promoters, immunogens and detoxicants, mostly of natural origin, processes and equipment for their manufacture and application practices, • launching industrial production of adaptation promoters, immunogens and detoxicants, mainly from Ukraine’s domestic starting materials, and • research and development of existing and new non-medicinal methods of health building and adaptation to anthropogenic loads, including ways to reduce immune reactivity of and risks to people subjected to adverse working environments, residing in heavily polluted areas or dealing with ionizing radiation and other negative factors at work.

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Non-ruled Market Economy as a Source of Chemical Terrorism

The latter concept implies providing local life support systems for unfriendly environments. By now, Ukrainian scientists and engineers have developed a variety of processes for potable water treatment by adsorption, electrochemical oxidation, electrocoagulation, electro-coprecipitation, electrodialysis, electrofloatation, floatation, membrane techniques etc. Each family must get small units for water purification, air cleaning and removal of hazardous substances from the food as soon as possible, for it may take decades to introduce cleaner production on a national scale. Here, we should follow the example of Western business people who bring with them to Ukraine devices enabling a safe existence in this unfriendly environment. More specifically, environment professionals in Dnepropetrovsk have offered a number of local CP projects. One of them is concerned with treatment of ash of the local steam power plant. According to Canadian experts, 32 elements may be recovered from the ash in addition to the residual coal, making the business of ash treatment highly profitable. There have been projects to produce building materials from the fly ash collected directly at precipitation filters. Moreover, this material attracted international entrepreneurs who wanted to export it to Spain, most probably for purposes of extraction of some rare earth metals. It is regrettable that no local business people took interest in the idea, especially when in Dnepropetrovsk area there are defense industry giants like Yuzhnyi Engineering Plant and Chemppri with their expertise in high technologies, including recovery of valuable metals and fabrication of appropriate sorbents and equipment. The steam power plant should become another site for an exciting project enabling a 2-fold reduction in the degree of flue gas cleaning while cutting the electric power consumption by a factor of 2 to 3. The new process that applies pulsed voltage to the precipitation filters has been successfully introduced at several other plants in Ukraine. These and other projects were included in the draft program of cleaner production for the Dnieper region. Each item in the program is backed with engineering and economic analyses. For many of the projects, international partners and prospective investors are sought that may gain profit by cleaning our environment. Coal is one of the major fuels in Ukraine where its environmental impact is much higher than that of nuclear energy, provided that there are no accidents. Yet there is no alternative to coal, for natural gas can only cover the most urgent household and industrial needs, not to mention the country's indebtedness for its imports. The question of environment-friendly combustion of coal is therefore highly topical. It is of special importance to the Lower Dnieper region where Pridneprovsk, Zaporizhia and Krivoi Rog steam power plants, Europe's biggest, are operated alongside with hundreds of smaller plants, cogeneration units and boilers. To abate pollution, one has to find its

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causes. With this in mind, a digest of recent materials found on the Internet is given in this issue. It has following sections: The environmental pollution in transition economy countries has reached critical levels. Vehicles, power plants, steel mills and nonferrous metallurgy works are the major air polluters. Pesticides are responsible for much of the harm done to human health. Water pollution continues on a large scale. Very often the situation is disastrous because this country has a combination of energy-intensive industries, thermal power generation, and intensive agriculture, further aggravated by Chernobyl. There is an urgent need to find feasible ways that would stop the ensuing depopulation in a lot of FSU countries, such ways to ensure survival that would work before the sustainable development concept has been implemented. In these times of a deep economic crisis, the economic and environment-related issues must be attacked simultaneously, in line with one strategy for a cleaner economy. This would be a change from a policy of anthropogenic impact assessment to that of at-source abatement of pollution. Such a program must be specific, realistic and not contradicting the idea of sustainability. It might be a program of cleaner industrial and agricultural production incorporating a systems principle of ascension from cleaner local units, mills, factories, and areas to a cleaner country to cleaner multinational regions. What makes this approach rather different from the mainstream international cleaner production (CP) movement is the desire to abolish the dominating “black-box” techniques. Instead of regarding a production facility as no more than a given set of benign inputs and polluting outputs, we insist that one should seek the best ways to affect a prospective cleaner object within the “black box”. As the major principle of cleaner economy, the systems approach is taken that deals with perfecting any nature-technology system at the various hierarchic levels, from environmental pollution sources to consumers, and takes into account the interactions and mutual effects of all important components. This type of analysis will reveal relationships between the ways to improve processes and the challenges of risk management and nature conservation. The main task is therefore to harmonize the nature-technology relation and, ideally, to engineer high-performance systems featuring desired environmental characteristics at each hierarchic level, so that the favorable environmental background is not impaired and, where possible, even restored. Following are the basic assumptions underlying the cleaner economy concept for transition economy countries: • At this time of a deep economic crisis, the economic and environmental challenges must be met simultaneously, in keeping with one strategy of cleaner economy. • A move towards a cleaner economy must focus not on consumption, but rather on perfecting those entities that are actual or potential polluters.

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Non-ruled Market Economy as a Source of Chemical Terrorism

• The success of a cleaner economy policy will be largely determined by the availability of professionals well trained in the theory and practice of “economy clean-up” and environmental management. No cleaner economy will be possible without creating a civilized • environmental market. The idea of restructuring in the area of material production to be based on: • developing a socially oriented market economy that would guarantee a proper life standard for the population, cleaner production, minimizing environmental loads, material • conservation, adoption of new types of activity grounded on environmentally safe technologies, • making a more balanced economy by shifting from production of means of production to consumer goods, and environmental impact assessment and auditing for all economic • projects. The macroeconomic transformations rely on changes in the structure of production and consumption, mainly in industry. This necessitates: • a more pronounced social orientation of industry to increase the relative importance of light and food-processing industries, • an effective combination of industry branches keeping abreast of international requirements and meeting domestic needs, • setting limits to raw material and semi-finished product industries, • stepwise reduction of exports from primary and other material- and energy-intensive industries, • increasing outputs of high-added-value products to facilitate effective utilization of domestic resources, and • restructuring the production environment via introduction of recent scientific accomplishments, conservation of energy and other resources, implementation of waste-free and environment-friendly technologies, application of optimized power sources, waste treatment and utilization. These points are common to the Sustainable Development Concept and to the cleaner production concept. How could all that be funded? It would be ridiculous to suggest that comprehensive actions towards a cleaner economy might be supported by the miserable national budget. There is even less reason to believe that any down-to-earth effort to upgrade some specific facility and implement advanced technologies and state-of-the-art equipment might be funded from it. Furthermore, we can hardly rely on the assistance from the West, and nobody here believes in assistance not backed by economic interest. What is to be done to make cleaner production profitable, as is the case in the West? One source might be those fines that are imposed on violators of environmental laws in transition economy countries. However, no mechanisms of channeling this money to environmental investments are available so far.

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All over the world, the environmental market is replacing punitive methods of environmental management and those environment protection agencies that are not capable of coordinating and managing cleaner economy projects. Worldwide, the taxation and payments for resources and emissions are devised in such a manner as to make it more profitable for the manufacturer to resolve the environmental issues in-plant, rather than to shift them off to the consumer area. A combination of sanctions with economic incentives for a cleaner production will make the latter not a recipient from, but rather a donor to the government budget. Yet even domination of a cleaner economy policy will not soon guarantee survival of the population under a deep economic crisis like the current one. The anthropogenic damage already caused to nature may prove too heavy and not lending itself to repair within the life span of one or even more generations. An analysis of the man-production-environment system reveals that for survival of human beings the CP concept must be complemented by two more lines of action, namely adaptation of human body to life in adverse conditions, and utilization of life support systems. The former approach implies development and implementation of biomedical and nonconventional methods for prevention of ailments, adaptation and rehabilitation based on recent scientific findings and combined efforts of scientists, engineers, educators and managers under a degrading environment in Ukraine. These are the major lines to be pursued: • setting up a tailored system of environmental education and training for the population in environmentally damaged areas, relying on the existing environmental education network and the media, • research and development of adaptation promoters, immunogens and detoxicants, mostly of natural origin, processes and equipment for their manufacture and application practices, • launching industrial production of adaptation promoters, immunogens and detoxicants, mainly from domestic starting materials, and • research and development of existing and new non-medicinal methods of health building and adaptation to anthropogenic loads, including ways to reduce immune reactivity of and risks to people subjected to adverse working environments, residing in heavily polluted areas or dealing with ionizing radiation and other negative factors at work. The regional program of adaptation and rehabilitation of the population is developed for the first time in the Ukraine as for near Dniepr river region, and in a kind of the concept is offered for any of a technogenous intense region. Feature of the program in integration of efforts on joint activity in spheres of a science, engineering, training and management with the purpose of decision of problems of preventive maintenance, adaptation and rehabilitation of the population in conditions of worsened ecological conditions in the Ukraine. Main directions of realization of the program:

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fulfillment of scientific researches on creation of adaptogenous, immunogenous (predominary a natural origin), techniques of their application, technologies and equipment for their manufacture; • fulfillment of scientific researches on ordering known and creation of new nonmedicine methods healthbuilding and adaptation of the person to technogenous effects; • creation of industrial manufacture of adaptogenous, immunogenous predominary based on Ukrainian raw sources; development and realization of the educational ecological programs • for all categories of the population. Main sections of the program: 1. Organization of a system ecological education and training of the population and realization of direct work in ecologically intense regions with use of a network of ecological training and mass media, 2. System engineering of diagnostic, adaptation, the increasing of the healthlevel and rehabilitation of the persons, received infringements of a health as a result of technogenous effects. 3. Fulfillment of scientific researches on ordering known and creation of new non-medicine methods of healthbuilding and adaptation of the person to technogenous effects, in particular, development of ways of immunity increase and reduction of the factors of risk at the persons, subjected to effect of harmful industrial factors, 4. Fulfillment of scientific researches on creation adaptogenous, immunogenous and other medicines for resistance against acting of harmful substances (predominary a natural origin), techniques of their application, technologies and equipment for manufacture. Survey of natural raw sources of adaptogenous, immuno-genous and development of industrial technologies and creation of its manufactures. 6. Development and introduction of new food products on the basis use natural byoaddings with adaptogenous and immunogenous properties, ensuring preventive maintenance of diseases ecological ethyology. 7. Development and organization of manufacture of an ecological engineering and surviving means. With arrival in Ukraine market economy it is possible to mark that many ecological problems both at the regional level, and at level of our country, were intensifyed. We have not while systematized analytical data about the change of concentrations of harmful matters in the water, air, soil, but of indirect indexes put a number on one's guard. But every year the population of Ukraine diminishes approximately on half-million persons, more anxious data about child’s death rate and morbidity. In Dnepropetrovsk to the end reasons are not found out of epidemic growth in the last years of quantity of pulmonary diseases. It is possible to consider as results of biotesting periodically intensifyed tendency to disappearance of populyatsii of sparrows in the center of city, Lately the complete disappearance is noticed practically in the town of cockroaches. But, speak, they are led even in the nuclear reactor...

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1.1. Processes of the Restructuring, Privatization, Military Conversion in the countries with transitional economy with account of market conditions. During Restructuring, Privatization, Military Conversion there is inconsistencies between requests of maintenance of sustainable development and problem of deriving of maximum profits. In the countries with transitional economy unfortunately there is slacking of state and municipal management and while there is not market mechanisms of managing of SMEs activity. Recently new program on Market Mechanisms and Incentives for Environmental Management (URL: http://es.epa.gov/ncer/rfa/02marketmech.html) as part of U.S. Environmental Protection Agency (EPA) and of its Science to Achieve Results (STAR) is announced. They are seeking applications for research leading to improved theoretical and/or empirical analyses of the feasibility and effectiveness of market mechanisms and economic incentives (MM&I) as substitutes for, or complements to, traditional environmental management programs. The terms 'market mechanisms' and 'incentives' refer to approaches that rely on economic incentives, market forces, or financial mechanisms to encourage regulated entities to reduce emissions, discharges and waste generation, or generally improve environmental performance. EPA is interested in supporting research on practical applications of MM&I approaches related to its mission, i.e., addressing environmental quality and human health.

1.2. Chemical Terrorism on local, national, and international levels (Source: A FOA Briefing Book on Chemical Weapons) There have always been fears that terrorists might be tempted to acquire and use weapons of mass destruction. The world received a shocking reminder of the potential impact of terrorist use of chemical weapons when the Aum-Shinrikyo sect used the nerve gas Sarin to attack civilian targets in Japan during 1994 and 1995. It is fortunate that, to-date, few other incidents of this nature have occurred. In the wake of the horrific terrorist attacks in New York on September 11th, 2001, fears of terrorist use of chemical and biological weapons were rekindled, and fueled by public release of information suggesting that the terrorists had considered using crop dusting aircraft in their plans. There is much that local, national, and international authorities can, and should, be doing to counter the threat of chemical terrorism. For an overview of specific subject of the protection against chemical weapons, it is necessary to pay attention on: • Decontamination

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Detection Protective Equipment Collective protection Protection against Chemical Weapons. There are four main cornerstones in the protection against chemical weapons, all of which are largely dependent upon each other to provide optimum effect. These four are: • physical protection: body protection, respiratory protection, collective protection, medical protection: pretreatment, therapy, • • detection: alarm, monitoring, verification, identification, all-clear, • decontamination: individual decontamination, equipment decontamination. An overview of chemicals defined as chemical weapons. Main Groups: • Nerve Agents Mustard Agents • • Hydrogen Cyanide • Arsines • Psychotomimetic Agents • Toxins Potential CW Agents • Today, only a few of these are considered of interest owing to a number of demands that must be placed on a substance if it is to be of use as a CW agent. • A presumptive agent must not only be highly toxic but also "suitably highly toxic" so that it is not too difficult to handle. • The substance must be capable of being stored for long periods in containers without degradation and without corroding the packaging material. • It must be relatively resistant to atmospheric water and oxygen so that it does not lose effect when dispersed. It must also withstand the heat developed when dispersed. • CW agents can be classified in many different ways. There are, for example, volatile substances, which mainly contaminate the air, or persistent substances, which are involatile and therefore mainly cover surfaces. All decontamination is based on one or more of the following principles: • to destroy CW agents by chemically modifying them (destruction), • to physically remove CW agents by absorption, washing or evaporation, • to physically screen-off the CW agent so that it causes no damage. Most CW agents can be destroyed by means of suitable chemicals. Some chemicals are effective against practically all types of substances. However, such chemicals may be unsuitable for use in certain conditions

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since they corrode, etch or erode the surface. Sodium hydroxide dissolved in organic solvent breaks down most substances but should not be used in decontaminating skin other than in extreme emergencies when alternative means are not available. CW agents can be washed and rinsed away, dried up, sucked up by absorbent substances, or removed by heat treatment. Water, with or without additives of detergents, soda, soap, etc., can be used, as well as organic solvents such as fuel, paraffin and carburettor spirit. Emulsified solvents in water can be used to dissolve and wash-off CW agents from various contaminated surfaces. Unfortunately, all these methods can not used in the case of global chemical terrirism of some modern “market” technologies are used in Ukraine. I would like to name only some of them on the example of our Pridneprovie Region: 1. During last several years one by one there are already 4 manufactures of the lead accumulators " Ista " adjoining directly to two inhabited files of city. I shall remind, that the building of new ecologically dangerous manufactures is forbidden in the technogenic overloaded city Dnepropetrovsk approximately 20 years ago. 2. Recently in the center of city Dnepropetrovsk it was utilization a lot of rockets “SS-20” (Program of USA – Ukraine) and we had the pollution in the air a lot of very dangerous and toxic geptil. 3. Using of the most cheap and therefore dirty and dangerous sorts of coal and liquid fuel (mazut) by our Pridneprovie Heat Electric Station, 4. And at last it is the using of the “special” Automotive fuel on the base of liquid wastes of coke factories of Ukraine, containing a carcinogen and drug benzol in quantities that are exceeding in other countries of Europe and world in tens times.

1.3. Automotive fuel on the base of liquid wastes of coke factories of Ukraine as the chemical terrorism factor. Recently Cleaner Production Center organized an Environmental Symposium on Transportation and Environment. In recent years, the number of cars in Dnepropetrovsk increased dramatically, predominantly owing to import of used cars, and exceeded 250,000 in 2000. Since the city has no by-pass highways, tens of thousands of cars pass its center daily. They run on cheap fuels containing massive admixtures of aromatic compounds like benzene, toluene and xylene. The fuels produced by cokeand-byproduct plants in Zaporozhe and Dneprodzerzhinsk contain 16

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times as much benzene as does US gasoline (1 to 2 %). In Kharkov, 100 gasfilling stations sell gasoline of unacceptable quality. The Security Service of Ukraine in Kharkov blocked an attempt of two local gasoline stations to sell adulterated gasoline. The hazardous fuel included the authentic A-76 grade heavily mixed with benzene, toluene and xylene to imitate high-octane grades A-93 and A-95. A good news, too. It is regrettable, however, that in Dnepropetrovsk very many, if not all, cars have to use fuels adulterated with these and other hazardous compounds. The practices of admixing them to gasoline have been carried on in this area for several years, in spite of numerous protests by concerned environmentalists in the media. This badly aggravates the environmental situation, already disastrous in the entire region. Xylene, benzene, styrene and toluene total to 40 to 60 per cent in most of the fuels, as reported by Dnepropetrovsk Sanitary Monitoring Station. The highway police, the air quality monitoring services or the meteorological stations do not measure the levels of these compounds. Although no reports on the amounts of the above aromatics in the exhaust gases are available, experts assert that complete combustion of these compounds in an engine is impossible. The combustion products therefore pollute the air to a degree that makes the common CO and CO2 pleasant air fresheners. No catalytic converter will help. Rather, it will be poisoned prematurely. Several measures may help remedy the situation with fuels: (a) to introduce new governmental specifications for the fuels to limit the aromatic contents, (b) to impose restrictions on sales of adulterated fuels based on more stringent control of fuel quality, (c) to carry out certification of bodies having a right to sell automotive fuel, (d) to put heavy environmental taxes on low quality fuel to be paid by both the producer and the distributor, (e) to get involved the governmental standardization bodies and consumer societies, and (f) to use state-of-the-art additives enabling a more complete fuel combustion and therefore improved environmental performance of vehicles. Only the latter option is workable at present, because the country is lacking oil. Following are some additives already in use in Ukraine. General-Purpose Fuel Modifiers T-4 and T-6 developed by A. Ozeryanskii in Kiev, Ukraine. Non-toxic agents that reduce pollutant discharges 1.5 to 3-fold and offer 8 to 15 % savings in fuel, depending on engine wear and fuel type, up to 30 % reduction in carbon monoxide, and 50 % less smoke, while increasing the engine power by 10 to 28 %. They are very simple in use, so that a 1.2-ml ampoule is just emptied into a fuel

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can. One liter of T-4 is enough to modify 18,500 l gasoline or 5,600 l diesel fuel. Its cost is 2 to 3 % of the fuel cost. Oil Modifier MP-8 of the same inventor reduces oil losses by a factor of 1.6, extends oil service life 2- to 3-fold and cuts pollutant discharges by at least 30 %, while enhancing engine power by up to 10 %. Also, this non-toxic additive reduces wear and varnish formation on engine parts and improves detergency and sealing. Its cost is about 40 % that of domestic motor oil. Some other developments may also prove useful for making combustion engines cleaner. Clean Air Valve developed by Ted Switen, USA. Tests on carburetor engines in Ukraine showed 2- to 4-fold reductions in the exhaust levels and fuel economy improvement by 1 %. At its prospective price of about $50, the device will pay back after a 15,000 to 20,000 km run. A modification intended for diesel engines will be run in in 1998. Ukrainian Catalytic Converter developed in Kiev. Being similar to its Western counterparts in performance, the device will be less expensive. Ukraine committed itself to the European Union that all its vehicles would be equipped with catalytic converters by 2003. Binary Fuel Device developed and produced on a full scale in Ukraine. Reduces hazardous exhausts by a factor of 2 to 3 through the use of a lowoctane gasoline plus propane-butene. The breakeven is predicted at 20,000 km. Yet another approach is to influence the combustion process itself by ionization, pulsed electromagnetic fields, glow discharge etc. The Institute of Energy at Dnepropetrovsk State University developed a plasma-activated sparking plug, currently in preparation for a full-scale production. Prof. V.N. Nabivach (Ukrainian State University of Chemical Engineering, Dnepropetrovsk). The levels of polycyclic aromatic compounds (PACs) in exhaust gases deserve special attention, for they often exceed maximum permissible concentrations 2 to 2.5-fold. A carcinogenic constituent like benzopyrene is million times as hazardous as CO and 50,000 times as harmful as NOx, an important difference being that its action is prolonged. The contribution of automotive engine exhausts to overall urban air pollution in Ukraine is approaching 30 %, a trend towards the 50 % in the West. In the absence of standards that would limit aromatics in automotive fuels, the coke and byproduct plants like those in Dneprodzerzhinsk, Zaporozhe and Avdeevka are free to produce fuels containing 50 to 70 % PACs, compared to "only" 30 to 40 % in the products of oil processing companies. PACs are fairly stable and tend to be adsorbed on building walls, trees etc., thus posing a permanent threat to public health. Another headache is dioxin, an extremely hazardous pollutant discovered in automotive exhaust gases in 1980s. A.G. Khandryga (Manager, Industrial Product Certification Dept., Dnepropetrovsk Center for Standardization and Metrology). We do certify

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the fuel that is imported whenever its quality is acceptable. What happens next, when it is unloaded into storage tanks and further on, is beyond our control. Only the Agency for Consumer Protection can request a certificate of quality directly at a gas-filling station. It may then see tens of certificates issued at different places. The law does not prohibit a distributor to apply to a certification center other than the local one. Furthermore, one check-up revealed that about 80 % of the certificates were forged. Prof. L.M. Pritykin (State Academy of Civil Engineering and Architecture of Dnieper Region). A rapid method to determine quality of gasoline is needed. The existing instruments generally measure octane number. This is not sufficient, for even with an acceptable octane number the exhaust gases may be highly toxic and the engine life short. Our effort was focused on a simple device for checking on gasoline grade. Our method uses 1 to 2 drops of fuel and takes 1 or 2 seconds to determine whether the gasoline really is of the labeled grade. The hand-held instrument does not need utility power and can be used in the field. It is fabricated in Ukraine and priced at $150 to $200. When the seller's grade does not correspond to the instrument reading, one should refer to more specific techniques for determination of the fuel fractional composition, octane number, chemical group composition etc. It is highly desirable to set up a center for fuel check-up on an absolutely independent basis. Such a center should be unbiased, self-standing and open to everybody. It might be run by the city executive committee but never by the commercial companies dealing in fuel. V.M. Golushko (Deputy Manager, Agency for Customer Protection). We have a right to check the quality of petroleum products since late 1997. We have inspected about 30 gas-filling stations and in 80 % of cases had to block the sales because of lacking certificates or poor quality. The problem of mixing various grades does exist but lends itself to control. Another potential trouble is the location of gas-filling stations that are often situated near the Dnieper River. No precautions against leaks are made. As Prof. V.M. Nabivach, Dr. V.A. Gerasimenko informed about problem of automotive fuel: quality and environmental safety, motor vehicle pollution is ever increasing, a great many hazardous compounds being discharged near the ground not only on highways but also in housing areas. Of all the ingredients of automotive fuel, aromatic hydrocarbons are the most toxic, benzene being the worst for its carcinogenic properties. Toluene and xylene have narcotic action. Fuel composition is a major factor that determines which compounds are present in the exhaust gases. Over 500 organic compounds have been reported in exhaust gases, including the initial ingredients and also polycyclic aromatics, of which 3,4-benzopyrene is the nastiest. The level of this carcinogen in exhaust gases increases with increased initial concentration of aromatics in the fuel. Other data suggest that lowering

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emissions of benzopyrene and fuel soot, its carrier, is the quickest way to a healthier urban atmosphere. The gasolines used in industrialized countries display high octane numbers while having no more than 43 % aromatics and up to 2 % benzene. As regards Ukrainian products, the respective values may be at 62 % and 4.6 % for gasolines produced by oil refineries and as high as 77 % and 26 % for products of coke plants. In order to achieve dramatic reductions in hazardous emissions to air in urban areas, it is therefore recommended that the domestic standards for gasoline limit benzene to 2 % and total aromatics to 45 %. As informed Dr. A.I. Korableva from Institute for Environmental Management and Ecology under the National Academy of Sciences of Ukraine in the report "Environmental impact of automobile transport by example of Dnepropetrovsk", Dnepropetrovsk with its annual discharge of air pollutants of 177,000 t (as of 1996) is among the worst affected cities in Ukraine. In these, the automobile transport was found to be responsible for at least 30 % of the total emissions which are 15 times the maximum permissible level. Aside from the dust, chemical, photochemical and noise pollution, there is the aspect of street washout of automobile-related pollutants into the River Dnieper. The measured annual receipts of lead, particulates and petroleum derivatives via rainwater and thaw water to the river are 0.45, 80,000+ and 1.8+ t respectively. The actual levels of petroleum derivatives in storm water sometimes were 206 times the maximum permissible concentration (MPC) for the fishery basins. At 34 km downstream from the city, the estimated levels of petroleum derivatives and particulates are 61 and 10.8 times the respective MPCs. The airborne lead is mainly accumulated in the soil of housing areas. And, at last, Prof. E.A. Derkachev, Dr. L.B. Ogir, Dr. A.A. Shevchenko, A.P. Shtepa, V.V. Sotnikov, V.I. Sviridov, G.P. Isaeva from Dnepropetrovsk State Medical Academy it their report "Hygienic assessment of automobile transport impact on the environmental situation and public health in Dnepropetrovsk" informed, that: 1. Soil, being one of the most stable elements of the environment, may serve as an indicator of long-time pollution with specific agents like heavy metals. 2. The distribution of lead in the soil in Dnepropetrovsk suggests that the pollutant is mostly supplied by automobile transport via exhaust gases. 3. Lead pollution level is predictive of a number of diseases in the affected population. 4. Reliable correlations were found between lead concentrations in the soil and the incidence rates in the population of Dnepropetrovsk. In the adults, the pollution levels were associated with complications in pregnancy and delivery, diseases of urogenital, nervous and bone-and-muscular system, blood problems and tumors. In the children, the blood, blood forming organs, respiratory system and the muscles and bones were most frequently affected.

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5. Comprehensive measures for abatement of automobile-related pollution in Dnepropetrovsk are needed. The Symposium adopted the following resolution that deems it necessary: 1) to introduce new governmental specifications for automotive fuels with a view to limiting the aromatic contents in harmony with international standards, to effect more stringent control of fuel quality and to impose restrictions on sales of adulterated fuels; 2) to implement state-of-the-art computerized systems for assessment and prediction of transportation effects on environment; 3) to carry out certification of bodies having a right to sell automotive fuels and to put a heavy environmental tax on low quality fuel to be paid by both the producer and the distributor; 4) to use state-of-the-art additives enabling a more nearly complete fuel combustion and therefore improved environmental performance of vehicles; 5) to highlight that accidents involving hazardous freights, particularly massive at railroads, are a challenge. According to the incomplete data available, hundreds of these occur at NIS railroads, so that one-time discharges of hazardous substances pose considerable threats to people and environment. The environmental monitoring of transportation is not up to the mark, advanced air purification and water treatment processes are not employed on a sufficient level, the waste management is inadequate, and the work on cleaner transportation has just started; 6) to consider as particularly urgent the problem of prevention and elimination of consequences of accidents in transportation of hazardous freights in the territory of Ukraine, and to develop proper techniques and facilities for the relevant transportation bodies; 7) to use the experience in environmental information monitoring gained by the Laboratory for Environment Protection at the Pridneprovskaya Railroad and to have the Ecotrans information retrieval system cover the entire railroad network of Ukraine; 8) to start R&D on waste management for the transportation companies; 9) to implement ideas and practices of constructive ecology, like closedcircuit water systems, on a broader scale; 10) to deem it necessary to gear Dnepropetrovsk Center for Standardization and the Consumer society to attack on the overall problem; 11) in view of the positive feedback from environmentalists in the region, to launch regular publication of Constructive Ecology and Business journal in 1999 and further on. To appeal to management of major industrial and transportation companies for support; and 12) to inform Dnepropetrovsk City Council, the Ministry of Transportation and the Ukrainian Railroad Company about the Symposium output and resolutions. Besides I would like to inform you about the current situation with automotive fuels in Russia, mainly in Moscow, and in Kazakhstan

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(Almaty) from the viewpoints of engine operation, fuel production, commercial trends and government regulation. International experience in these fields is also covered. Considering the quality of fuels available in Russia (and Ukraine), ways to achieve a more nearly complete combustion are to be preferred to reliance on catalytic converters. A number of additives are covered, including the following ones produced in Russia: Molilat: Lubricity additive containing molybdenum disulfide for improved resistance to wear, pitting and fretting. Reduces noise, increases maximum speed and engine life and cuts fuel consumption. Molilat-2M: Metal-depositing additive for recovering compression in the cylinders and pressure in the lubrication system of worn engines. Improves power performance, saves fuel and oil, reduces noise and smoking of the exhaust. Guaranteed compatibility with all mineral oils. Udav: Lubricity additive applicable for new and old engines alike and compatible with any mineral lubricant. Contains ultrafine diamond powder for special friction. Reduces noise, wear and smoking while improving power and extending engine life. Aspekt-Modifikator-U: Single-use agent which produces a thin porous film capable of retaining lubricant on the surface of engine and transmission components. Reduces noise, wear, varnish formation and fuel consumption and improves detergency. Aspekt-Modifikator: Versatile fuel additive that neutralizes water, prevents corrosion and ice formation in the fuel system while improving engine environmental performance. RiMet: Lubricity additive for motor and transmission oils. Contains ultrafine particles of a special alloy. Reduces wear and smoking, cuts fuel and oil consumption and improves compression. Turbo-Oktan 115: A small-pack version of Feterol for increasing the octane number directly in the fuel tank. The agent eliminates detonation, enhances power and extends engine life while its excess of oxygen improves combustion and thus reduces pollution. Forum: Wear-preventive additive containing polytetrafluoroethylene particles 0.4 micrometers in diameter. Dramatically reduces noise and oil loss. As for Ukraine, it has Renoks, an antidetonation modifier developed by Prof. Yu. Merezhko of the Ukrainian State University of Chemical Engineering in Dnepropetrovsk. It offers a 1.5 to 2-fold reduction in pollutant emissions and an 8 % cut in fuel consumption at the cost of 1.0 to 1.5 % of fuel price. Also available are Remol-2 and Remol-2A produced by Remol in Odessa. These oil additives can be recommended for both carburetor and diesel engines after 40,000 km run to recover and stabilize compression, save up to 8 % fuel, protect engine components and reduce hazardous substances in exhaust gases. The multipurpose fuel modifiers T-4 and T-6 produced by ADIOZ company of Kiev were covered in the previous issue. Mazut fuel emulsification. The Dnepropetrovsk national university for a number of years deals with the complex problems of

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power system connected to economy of fuel and protection of an environment. In this sense the direction connected to use water-fuel emulsion is perspective. Within the framework of this direction emulsification systems for liquid fuel are developed in view of individual conditions of the customer. The systems developed by their emulsification fuel are successfully maintained on some enterprises of Ukraine. The known data are put in a basis of development on an intensification of process of burning and reduction of toxic emissions at burning in furnace (the chamber of combustion) water-fuel emulsion. The comparative data on burning waterless and emulsified fuel show, that emulsified fuel burns down much faster waterless, thus burning water-black oil emulsion in furnaces provides economy of 10-15 % of black oil in comparison with burning of clean fuel. Besides one of the factors determining efficiency of use water – fuel – emulsion (WFE) in котельно-топочных processes, the opportunity on their basis is to solve a number of environmental problems. WFE burning reduces a pollution emissions of NОх in gas (approximately on 50 %), approximately in 3-4 times reduces emission of carbon black adjournment, reduces emissions of benzapirene in 2-3 times, etc. The greatest economic benefit and simultaneous decrease of gas emissions provides addition in fuel of 10-15 % of water, and the greatest ecological effect regarding recycling the waters polluted with organic products is realized at a level of a water phase up to 50 %. The physical features of burning distinguishing WFE as new fuel in comparison with known, are defined substantially by imperfection existing sprayer devices. The last practically are not capable to provide dispersion of liquid fuel on a level of dispersiveness of less than 100 microns. At the same time the drops of emulsion with such size, created by sprayer devices contains some thousand micro- drops of water. To this in a high-temperature zone of furnace chambers the drop of emulsion blows up and occurs secondary dispersion fuel. This effect is especially important at burning coal pitch and heavy extra-heavy oils used in metallurgy. As a result of such microexplosions in furnace there are centers of turbulent pulsations and the number of elementary drops of fuel due to what the torch increases in volume increases and in regular more intervals fills the furnace chamber that results in alignment of a temperature field of furnace with reduction of local maximal temperatures and increase in average temperature in furnace; to increase of luminosity of a torch due to increase in a surface of radiation; to essential reduction underburning of the fuel; allows to lower quantity of blown air and to reduce connected with it heat loss. Simultaneously in a torch occur the catalytic reactions conducting to reduction of harmful gas emissions. The opportunity of reduction of quantity of blown air at burning water-fuel emulsions is rather important, as according to skilled given efficiencies of the boiler unit at reduction of factor of surplus of air on 0,1 increases for 1 %. And at last I would like to inform you about our proposals at Systems approach to cleaner transportation using. The transportation-

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highway complex is a major air polluter, with the motor vehicles accounting for about 70 %, the rolling stock 25 %, the aircraft 2 %, the road-building machines 1.4 % and the vessels 1 % of the total transportation-related pollution. The morbidity in urban areas was found to correlate with the size and intensity of operation of the vehicle fleet. In rural areas, carcinogens originating from vehicle exhaust gases tend to accumulate in plants grown near highways. The general issue of cleaner transport may be approached using the approximation of a closed system including man, nature and transport in which various feedbacks and feedforwards exist between all subsystems. Following specific environmental problems may further be recognized that relate to: running gear, engines,fuels,cargo carriage,cargo reloading, passenger compartments, infrastructure, and accidents. The systems approach applied here enables treatment of hierarchic levels for each specific type of transport. A quantitative characteristic of environmental safety and an algorithm of environmental safeguarding is suggested that may help find and select the best engineering solutions. The algorithm includes the following steps: 1. Processing the initial information to determine the appropriate hierarchic levels and especially those that control the pollution. 2. Selecting methods to influence the system. A major aspect of environmental safeguarding is the abolishment of «bulk» neutralization of pollutants in a mixed fluid flow. It must be replaced by local action taken, wherever possible, on a component-by-component basis as close to the origin as may be, and preferably inside the source. This is just the opposite of currently prevailing systems where the entire spectrum of pollutants are collected and neutralized and/or recycled. Moreover, the local treatment performed close to the source is less expensive, if one takes into account all relevant costs. Since vehicles mostly rely on combustion for their energy, the safeguarding methods will include: - minimizing residence time and providing an excess of one of the reagents, resulting in reduced formation of side products, - recuperation or looping of the matter and energy flows enabling a more nearly ideal combustion and reduced rates of side processes, - heterogenization to suppress formation of side products by the removal of the target product from the reaction zone at the instant of its formation, and adaptive processes and hardware for more reliable operation due to improved flexibility, helping reduce discharges during idle running and acceleration. 3. Engineering and economic analysis of the available safeguarding approaches and methods. 4. Selecting the economically and environmentally optimal safeguarding alternative.

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Non-ruled Market Economy as a Source of Chemical Terrorism 5. Making request for proposal to design the safeguarding system

adopted. 6. Preparing a business plan to carry out the safeguarding project. Any comprehensive project to process wastes and side products should not be developed before the completion of the safeguarding designing for the transportation system. The most effective direction for ecologization of the fuel burning process is the use of water- fuel emulsions with the soluble in water catalytic non- corroding additions and ultrasonic mixing by the sharp superheated steam. At development of our suggestions we came from that fact, that exhaust gases of combustion engines contain a generous amount of the organic and inorganic compounds, distributed between the gas phase and phase, being microparticles, 90% from which have sizes less than 1 mk. These particles are adsorbed on its surface of hundred chemicals, including mutagennie and carcinogenic matters. Mass of these particles is very small, and therefore its are inhalable dust. A gas phase contains, including benzapiren and oxides of nitrogen, which are predecessors of acid rain. These exhausts cause at man the allergic reactions and can lead to different pulmonary and cardiovascular diseases, including the cancer. Decreasing of the oxides of nitrogen and microparticles emissions, traditionally includes the use of catalytic converters. These methods are very difficult and require the large capital investments, that limits their commercial applicability. Addition of water to the fuel, multiplies mass of the air-fuel mixture, entered in time unit, resulting in the improved dispersion and mixing.The improvement of interfusion causes more high speed of freed of heat and growth of pressure, that results in formation of more high maximal pressure in the combustion chamber of engine. Water also lowers a spades temperature of burning fuels, that in same queue conduces to the diminished formation of oxides of nitrogen. Reduction of the formation of oxides of nitrogen proportionally to maintenance of water in fuel and relies on many factors. Addition of 8-25% water allows to decrease of CO emission to 40-70%, soot - to 40-60%, heavy hydrocarbons (including benzapiren) – to 70%. Unlike the known approaches we develop the use of water- fuel emulsions with the soluble in water catalytic non- corroding additions and ultrasonic mixing by the sharp superheated steam for reduction of the oxides of nitrogen and soot emission in the combustion engines. Our know how is also the use of the electro-activated water for emulgation. The first results testify the technical and economic expedience of the chosen direction.

Subject Index A Acetylcholinesterase, 245, 249 Acetylthiocholine sensor, 247, 248 Advanced Concept Technology Demonstration, 92 Aerosol Time-of-Flight Mass Spectrometry, 119, 127 Aflatoxin, 39, 40, 253, 269 Amperometric biosensors, 236 Anatoxin, 38, 44 Antibodies, 232, 262, 298 AnzenBio, 89 ATOFMS system, 121, 122, 127 Autonomous Pathogen Detection System, 67, 104 Azospirillum brasilense, 149, 157, 160 B Bacillus anthracis, 20, 120, 125, 143 Bacillus subtilis, 121, 123, 125, 126, 127, 139 BESOI wafers, 276, 279 Bioaerosol, 70, 121, 128 Biological Aerosol Sentry and Information System, 91, 94 Biological warfare agents, 119, 208, 262 Biosurveillance system, 21 Biotinylated polypyrrole films, 170 BioWatch defense system, 91 Botulinum toxin, 31, 32, 33, 209 Brucellosis, 54 C CD-Spectrometer, 332 Cell Physiometry tools, 129 Chem.-Bio Emergency Management Information System, 97

Chemical detectors, 210 Chemical warfare agents, 245 Choline esterase, 237 Choline oxidase, 237 Communications and Information Technology, 52 Crimean–Congo hemorrhagic fever, 51, 53 Cyanobacterial toxin, 36, 44 D Dielectrophoresis, 130, 131, 142 DNA hybridization, 166, 190 DNA LCD, 308, 309, 310, 311, 312, 313, 317, 318, 319, 320, 325, 327, 329, 332, 333 DNA-probe, 120 DNAzymes, 200 Domestic Demonstration and Application Programs, 91, 93 Drug, 44, 108 E Electronic nose, 271 Electro-Optical Analyzer, 145, 216 Electropolymerized films, 165, 172 EO spectral analysis, 152, 154 Epidemiology and Surveillance, 52 Escherichia coli, 132, 142, 147, 149, 160, 163 E-SMART® program, 216 Euglena gracilis, 141 F Francisella tularensis, 143, 221, 222, 223, 228, 229, 231, 232

SUBJECT INDEX

336 G GMP standards, 107 Gram-positive bacteria, 133 H hand-held electrochemical biosensor, 213 herpes, 51, 53 human chorionic gonadotropin, 214 human luteinizing hormone, 214 I Immunochromatographic test-system, 298 Infectious diseases, 9 Integrated, 51, 52, 186, 196, 262 ISFET chip, 277, 278

multichannel electrochemical biosensor, 225 multichannel optical detector, 218 Multiple Displacement Amplification, 89 Mycobacterium tuberculosis, 291, 292, 299 mycotoxin, 45 N Nanobiosensors, 175 Nanomechanical biosensors, 175, 189, 191 Nanotechnology, 142, 196 Natural toxins, 29, 30 Networked biosensors, 219 Newcastle disease, 53 O

J

Optoelectronics biosensors, 175

K

P

kolibacteriosis, 51, 53

parovavirus, 51, 53 Pelikan system, 264 Pesticides, 235 phage transfection, 154 phosphoorganic chemical weapons, 292 phosphoorganic insecticides, 292 photopatterning, 166 plague, 51, 52, 53, 208, 209 polyelectrolytes, 241, 291, 292, 293, 295, 296, 297, 301 polymerase chain reaction, 73, 83, 100, 120, 219, 222, 231, 232 Potentiometric biosensor, 236 PROACT program, 91, 97, 98, 102 Promega’s MagneSil® technology, 88

L laboratory-on-a-chip, 22 Laser, 119, 120, 128, 216, 217, 218 Laser-Based Point Detector, 216, 217 Legionella pneumophila, 291, 292, 299, 300 Liquid crystalline dispersions, 306, 333 M M. lysodeikticus, 133 Mach-Zehnder interferometer, 175, 176, 183, 185, 186, 195 MALDI-TOF-MS, 120 microarray technology, 207, 212 microbead-based assays, 72 Microcantilever biosensors, 175, 177 microelectronics technology, 22, 175, 176, 188 Militarily Critical Technologies List, 19 Molecularly Imprinted Polymers, 267, 271 MS spectra, 125

Q Quality assurance, 116 Quality control, 107 Quality Policy Certification, 105 R Ricin, 33, 34, 43, 208 rotavirus, 51, 53

SUBJECT INDEX S salivary peroxidase, 214 salmonella, 9, 54 salmonellosis, 51, 53 Sample collection, 78 Saxitoxin, 35, 36 Screen-printed electrode, 247 Secure and Sustainable Disease, 51, 52 self assembled monolayers, 274 sensor array, 273, 274, 275, 276, 279, 280, 286, 288 sequential injection analysis, 71 silicon cantilevers, 191 SpinCon® technology, 80 Staphylococcus aureus, 295 Surface Plasmon Resonance Sensor, 175, 176, 195 Surveillance System, 51, 52 T TaqMan assay, 74 Telomerase, 203 testing requirements, 106

337 thermocycler, 74 tick-borne encephalitis, 51 Total Internal Reflection, 179 Toxins, 44, 208, 209, 269 triazine herbicides, 292 tryptophan, 124, 125 Tularemia, 104 U Universal Mobile Telecommunications System, 178 UNMOVIC, 48, 49 UNSCOM, 47, 48, 49, 50 UV-LIF, 217, 218 V Validation testing, 106, 108, 109 viruses, 18, 20, 29, 54, 72, 87, 99, 120, 148, 176, 208, 215, 233, 241, 292, 294 W West Nile Fever, 18, 22, 55