Science for Peace and Security Programme
Multi-year Projects
NPD: Dr. Matteo GUIDOTTI, CNR-ISTM
Milano, ITALY
PPD: Prof. Mykola STARODUB, Nat. Univ. Life and Env, Sciences,
Kiev, UKRAINE
Prof. Andrew KATSEV, Crimean State Medical Univ.
Simferopol, UKRAINE
Dr. Chiara BISIO, Univ. of Eastern Piedmont,
Alessandria, ITALY
Conventional Decontamination
Conventional decontamination is based on:
- Dissolution
organic solvents, petrol, paraffin, etc.
- Removal
bentonite, magnesia, absorbing powders
- Destruction
basic solutions, detergents, chlorinated lime, decon solutions
- Combustion
• Both physical and chemical actions
• Large amounts of water
• Oxidising agents
All these methods need huge amounts of reactants and/or energy and
pose several problems in terms of safety, environmental and economical
sustainability, costs and disposal of the detoxified by-products
• Formation of hazardous by-products
as dangerous as Chem Bio agents
Current status and needs
a reliable catalyst must be
1) robust, under re-use conditions 2) cheap, for production and scale-up 3) active, as immediate as possible 4) selective, avoid hazardous by-products 5) versatile, for a wide range of aggressives 6) safe and non-toxic 7) effective under mild conditions, as close as possible to ambient conditions
From
stoichiometric to
catalytic decontamination
Main Objectives of the Project
- Development of effective, cheap and reliable nanostructured inorganic solid systems for the catalytic decontamination of chemical warfare agents (CWA) - Evaluation of the large-scale use of these materials in decontamination devices, assessing their toxicological impact on living organisms by rapid and reliable biological tests
CNR – Institute of Molecular Sciences and Technologies (ISTM)
National University of Life and Environmental Sciences of Ukraine
(NULES)
University of Eastern Piedmont (NanoSISTEMI)
Crimean State Medical University of Ukraine
(CSMU)
- testing of solid catalysts in liquid-phase catalytic oxidation of nerve agent and blistering agent simulants
- Preparation of nanostructured synthetic clays and inorganic nanostructured oxides
- Physico-chemical characterization of solids
- Development of biosensors and enzymatic methods for toxicity
assessment -Evaluation of toxicity on health and
the environment
- Estimation of toxicity (ecotoxicity) of all species will be estimated using
bioluminescent bacteria technology.
The Participants
Transdisciplinary approach to the problem
Phase 1: Design, synthesis and characterization of nanostructured metal-containing inorganic oxides
Definition and selection of materials Synthesis and characterization of nanostructured oxides and layered materials nanometric oxides (Al2O3, TiO2, ZnO, WO3 or MgO) layered solids (smectite clays: saponite and hectorite)
Preparation of metal-supported inorganic catalysts single-site catalysts containing redox-active centres (Ti, Nb, V, W, Fe, ...)
Silicon Aluminum Oxygen Hydroxyl
M n + • X H 2 O
~ 1 nm
Nanostructured TiO2
Synthetic clay
Phase 2: Testing the materials in the oxidative decontamination of a blistering agent simulant and of a nerve agent simulant
Catalytic tests on the detoxification of blistering and nerve agent simulants CWA simulants for evident health and safety reasons
Study of the chemical mechanism of the catalytic oxidation on the most promising solids
Catalytic evaluation of selected materials under real working conditions with genuine CWA in collaboration with CeTLI Italian Armed Forces Technical Centre
ClS
ClS
Cl
CEES
Sulfur Mustard
P
O
OO P
O
F
O
DMMP Sarin
Environmentally friendly oxidants
H2O2, O2, air
Phase 3: Optimization of biosensor methods for the evaluation of environmental and toxicological impact.
Development of enzymatic biosensors for the determination of organophosphorous substances
Elaboration of optical systems for the express evaluation of the total toxicity with living micro-organisms determination of chemiluminescence of Daphnia magna
Development of a biological system for the express control of the effect of CWA degradation products on vegetables “Floratest” to estimate the influence of toxics on plants
Development and validation of a special cytological test for the control of mutagenic effects of CWA simulants by-products
Models of multi-electrochemical
biosensors
Daphnia magna
Phase 4: Environmental and toxicological impact of the solids and on the decontamination by-products
Toxicological evaluation of selected materials impact of nanosized solids on living organisms
Determination of the total toxicity of CWA simulants after detoxification treatment evaluation of side-production of hazardous compounds
Estimation of the possible mutagenic effects of selected materials “Studying chronic effects on living organisms
Evaluation of the effect on vegetables
NanoHazard ? Nanotoxicology ?
Portable chronofluorometer “Floratest”
Implementation of the Results
• Publications and presentations at international level (peer-reviewed journals and international congresses on CBRN topics)
• Deliverables in form of demonstrators
the preparation on multigram-scale of at least two solids for the total and safe detoxification of CWA (blistering and nerve agents)
will be the most relevant deliverable
real application to new tools for CBRN Defence
• Patents for the most promising findings in catalytic materials and novel biosensors and detection tools
• Communication Plan Internet website, divulgation papers and video through NATO Press
media office (dual-use of Chemistry)
strong contacts with OPCW, IUPAC, Italian Society of Chemistry and National Academy of Sciences of Ukraine
Nanosized metal oxides
Nanocatalysts for abatement
Key role of homogeneously dispersed and
accessible oxidation and acid
sites
Abatement of CEES (chloroethyl ethyl
sulfide; HD mustard simulant) in the
presence of H2O2 over Nb-containing saponite
clays
0 5 10 15 20 25 30
0.0
0.2
0.4
0.6
0.8
1.0Blank
Na-SAP
H-SAP
Na-NbSAP-Et
Na-NbSAP-Cl
NbSAP-Cl
NbSAP-EtCE
ES
mo
lar
ratio
Time (h)
Oxidative degradation of CEES
at 25°C with H2O2 (70mM)
to be published soon work in progress for toxicological evaluation
Relevance to Security Issues
• Fully consistent with the Key Priorities of the SPS Programme
(1.d) Defence against CBRN Agents
(1.d.i) Methods and technology regarding the protection against,
diagnosing effects, detection, decontamination, destruction, disposal and containment of CBRN agents
Strengthen national and international preparedness and response to non-conventional threats
Improve security in terms of 1) reduced risks of illegal uses (better prevention)
2) reduced vulnerability for the civilian population (better protection) 3) improved risk management (minimization of negative
consequences).
Valid for NATO countries, but particularly relevant for Italy and Ukraine, in its strategic role between European and Asian scenarios
Strong points of the Projects
Transdisciplinary approach to the problem
Large participation of young researchers
Safety issues for nanosized compounds - “Nanotoxicology” NanoREG
Cradle-to-grave evaluation
Deep interest by governmental end-users in Ukraine, Italy and USA
Focus on one well-defined final product - tool for decontamination of CBRN agents
• What research in CBRN Defence requires urgent and substantial
attention?
• problem of dual use (for peaceful or illicit purposes) of emerging
disciplines (nanosciences, nanotech, biotech, information tech,
cognitive sciences) is real and is a source of concern.
• New scientific advances mean new technological capabilities to set up
unexpected threats to global and/or local security.
• A strategic study of the potential misuse of new discoveries should in
developing adequate countermeasures to new threats.
Way Forward – SPS CBRN
“Traditional” non-toxic
compounds
Nanosystems as new aggressives
Risk of uncontrolled production of nanosized hazardous compounds
Nanoshaped or nanosized
materials
Results within parameters
NO VIOLATION
OF REGULATIONS
Uncontrolled manufacture
National or international “traditional”
analytical control
Novel hazardous
or toxic materials
OK for production
No macroscopic difference in chemical composition between the “raw material” and the final product
• What should be the focus of the SPS Programme in CBRN
Defence?
Way Forward – SPS CBRN
• “Preventing is better than curing”
• Not only support to pure and applied research or high-level
specialization, but also to fundamental education and formation
about the ethical use and study of Sciences
• NATO-ASI or ARW Books are fundamental textbooks at graduate
level too
• A plan for discussing and highlighting these fundamental issues should
deserve more attention, at educational level with schools and
universities
• Ideas for potential SPS activities in the CBRN field (according to
your expertise)
• Converging efforts
Academy, Education institutions, First
Responders, Military, Industrial manufacturers
• These are domains that possess top-level
capabilities but that, too often, do not interact
• National Scientific Societies, IUPAC, OPCW are
already active to bridge the gap
Way Forward – SPS CBRN