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?