Dustin EwardBiologist, International Programs
Edgewood Chemical Biological Center
DEVELOPMENT OF A DEVELOPMENT OF A MULTINATIONAL TICs & MULTINATIONAL TICs & TIMs RISK ASSESSMENTTIMs RISK ASSESSMENT
Collective Protection Conference21 June 2005 ▪ Monterey, CA
Introduction
Chlorine
“Weapon of Opportunity”
1993
Bosnian Civil War
1994 – Determine whether a hazard existed concerning the release of industrial chemicals in a military situation
GOAL: Develop criteria for assessing the hazard posed by TICs in order to identify industrial chemicals that could be readily modified for military applications
Toxic Industrial Chemical:1) LCt50 < 100,000 mg-min/m3
2) > 30 tons produced/year at one production facility
Examined TICs:
1) Appreciable vapor pressure at 20oC, or 2) Listed in the USDOT Emergency Response Guide
Past International Efforts in TICs
98 TICs placed into the three hazard categories:
Created a Hazard Index (HI) to rank the TICs:
HI = (toxicity)x(state)x(distribution)x(producers) = maximum value of 625
- not likely a hazard unless specific operational factors indicate otherwise
- indicates a TIC that may rank high in some categories but lower in others such as number of producers, physical state or toxicity
- widely produced, stored or transported- highly toxic, easily vaporized
HI<35
36<HI<80
HI>81
Low Hazard
Medium Hazard
High Hazard
Past International Efforts in TICs
HIGH=21HIGH=21 MEDIUM=41MEDIUM=41 LOW=36LOW=36
AmmoniaArsineBoron trichlorideBoron trifluorideCarbon disulfideChlorineDiboraneEthylene oxideFluorineFormaldehydeHydrogen bromide
Hydrogen chlorideHydrogen cyanideHydrogen fluorideHydrogen sulfideNitric acid, fumingPhosgenePhosphorus trichlorideSulfur dioxideSulfuric acidTungsten hexafluoride
Past International Efforts in TICs
Chemicals identified as “High Hazard”
NA5Not specified
Yes – arsenic, cyanides, phosgene, metals13Other chemicals
Yes – RDDs (Moscow)1Radioactive
Yes – IEDs1Dusts
Yes – Oklahoma City bomb2Fertilizers
No2PCBs (slow onset)
Yes – Bhopal (sabotage)3Pesticides, including precursors
No3Plastics manufacture
Yes – Abortion Clinics6Acids & Bases
Yes – Kutina, Croatia6Ammonia
Yes – Texas, Columbia, Guatemala, Kuwait7Oil
Yes – Jovan, Croatia8Chlorine
Yes – Kutina, Croatia8Petrochemicals
Yes – Animal Rights & Environmental Arson8Liquid fuels
Yes – Oklahoma City Bomb12Explosives
Yes – Columbia, 200015Fuel gases
Ever Used as WMD?Frequency (%)Chemical Class
KEY LIMITATION: Toxicity was the principal inclusion parameter
Past International Efforts in TICs
Recent International Work
2002 - effort to reexamine past multinational TICs/TIMs work
Concept of hazard expanded to include:CorrosivenessReactivityFlammability
Use a Risk Management Approach
Look at pesticides that, due to low vapor pressure, were excluded from previous work
The following chemicals need assessment:High Production Volume (HPV) chemicals on the Organization for Economic Co-operation and Development (OECD) list - 5,235 chemicals
Produced or imported > 1,000 tons/year by at least one OECD member country
HPV fuels and pesticides on the UN Transport List
Nationally regulated chemicals (by EPA and other agencies)
Chemicals Assessed
Data is the limiting factor in assessment
PesticidesMost are of 3 classes:
Organophosphorus (OP) (low volatility liquids)− most important in terms of a potential military hazard
− cannot convert into “established” nerve agentsCarbamates (low volatility solids)Coumarin derived anticoagulants (solids)
High percutaneous toxicity
Impurities may be the major human hazard for some
Most (except fumigants) have volatilities << GB
29 listed by the World Health Organization (WHO) as extremely hazardous, 61 as highly hazardous
Risk Estimate
LowLowLowLowModerateNegligible
LowLowModerateModerateHighMarginal
LowModerateHighHighExtremeCritical
ModerateHighHighExtremeExtremeCatastrophic
UnlikelySeldomOccasionalLikelyFrequent
ProbabilityHazard
Risk Assessment Matrix
Severity of Hazard Ranking (SH)
SH = maximum toxicity (T), flammability (F) or reactivity (R)
indicates relative hazard for three hazard categories
Toxicity ranking based on a modified EPA procedureindicate most serious hazard by exposure route
National Fire Protection Association (NFPA) values used for flammability and reactivity
additional chemicals assigned flammability rankings based on NFPA procedure
SH Classes
T F Rtoxicity (oral) flammability
sulfuric acid 7664-39-9 4 0 2 toxicity (inhalation) catastrophicacetylene 74-86-2 1 4 3 flammability catastrophic
nitromethane 75-52-5 1 3 4 reactivity catastrophicphosgene 75-44-5 3 0 1 toxicity (inhalation) criticalmethanol 67-56-1 1 3 0 flammability critical
Severity of Hazard
1 catastrophic
Chemical CAS No. Hazard Score
hydrogen cyanide 74-90-8 4 4
Primary Hazard
4320 or 1RANKING SCORE(Max F, T, I scores)
CatastrophicCriticalMarginalNegligibleSEVERITY OF HAZARD
Probability of Encounter Ranking (PR)Probability Ranking (PR)= (physical state) + (production) + (history)
Where:
Physical state (solid, liquid, or gas) is scored as 1, 2, or 4, respectively
Worldwide production, based on # of countries producing/selling/distributing the chemical, is scored 0-4
History of association with intentional or accidental catastrophic incidents scored 4, 3, 2, or 0
PR Scoring/Classes
0-30
4-9Solid1
ROTA10-18Liquid2
Scheduled Precursor19-393
Used Intentionally> 40 (max 72)Gas4
HistoryNumber of Producing CountriesPhysical StateScore
7-9
Likely
10-124-62-30 or 1RANKING SCORE
FrequentOccasionalSeldomUnlikelyPROBABILITY OF ENCOUNTER
40
Extreme
800257256247Number of Chemicals
TotalHighModerateLowRISK
Principal Hazard for the 40 Extreme Risk Chemicals
222214Number of Chemicals
InstabilityFlammabilityFlammability & ToxicityToxicityRISK
Risk Assessment
Extreme Risk ChemicalsToxic Chemicals Not Previously Highlighted:
17
22
11
19
21
47
6
Number of Producing Countries
LikelyCatastrophic4 (Oral)LiquidPhosphoryltrichloride
LikelyCatastrophic4 (Inhalation)GasCarbon monoxide
LikelyCatastrophic4 (Oral)SolidPotassium cyanide
LikelyCatastrophic4 (Oral/Dermal)SolidSodium cyanide
LikelyCatastrophic4 (Oral/Dermal)LiquidAcrylonitrile
LikelyCatastrophic4 (Dermal)LiquidBenzene
LikelyCatastrophic4 (Oral/Dermal)GasParathion
Probability of
Exposure
Severity of HazardToxicity ScorePhysical
StateChemical
58
68
18
Number of Producing Countries
LikelyCatastrophicFlammabilityGasHydrogen
LikelyCatastrophicFlammabilityGasAcetylene
LikelyCatastrophicInstabilityS/LNitroglycerin
Probability of
Exposure
Severity of Hazard
Principal Hazard
Physical StateChemical
Flammable/Instable Compounds:
ATSDR ApproachAgency for Toxic Substances and Disease Registry (ATSDR) approach used as a quality control check
Builds on UN Transport of Dangerous Goods Model Regulations
Why use transportation data?
– Utilize previously developed, internationally accepted standards
– Chemical disasters occur:49% fixed facilities46% transport5% transfer points
– Includes common hydrocarbons
ATSDR Approach
Substances presenting low danger
Substances presenting
medium danger
Substances presenting
high dangerDescription
IIIIIIPacking Group
UN Packing Groups
ATSDR Risk determined according to the equation:Risk = (max hazard) + (frequency) + (physical state) + (history)
Maximum Hazard = max value of primary hazard assigned by Packing Group Number
Frequency = % of shipments + % of tonnage of dangerous goods shipments
Physical State = same as initial assessment
History = same as initial assessment
ATSDR Approach
Solid<10%1
ROTALiquid10-25%Packing Group III2
Scheduled Precursor25-100%Packing Group II3
Used IntentionallyGas>100%Packing Group I4
HistoryPhysical StateFrequencyMaximum HazardScore
A total of 2796 materials were assessed:
141497433771Number of Materials
LowerMediumHighVery HighRisk
6-49-711-1012-16Risk Score
Limitation: Frequency data is for chemical classes, not individual chemicals
Value: 25/40 “extremely high” risk chemicals ranked “very high” in ATSDR Assessment
Specifically addressed pesticides, identifying 1 as an “extreme risk” and 23 as “high risk”
Key OutcomesPerformed a Risk Assessment ranking 800 chemicals and identifying 40 which present an “extreme risk”
This assessment remains a primary resource for TICs & TIMs information for the DoD and a
host of other government agencies
Used ASTDR approach as a quality control check
Questions?