Neutralization of VXNeutralization of VXUsing Unclassified Information from the Newport project
American Chemical Society MeetingDecember 4, 2003
P d bPresented by:
Scott S. Haraburda, PhD, PEAssistant Project ManagerNewport Chemical Agent Disposal FacilityE-mail: [email protected](765) 245 6097 ( i )
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(765) 245-6097 (voice)(765) 245-5980 (facsimile)
Agenda
N t Ch i l D t (NECD) I f ti
g
• Newport Chemical Depot (NECD) Information
• VX Nerve Agent Information
• Neutralization Process
• Protection Used to Ensure Safety
• Haraburda Project Leadership Rules
• Questions ???Q
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Newport Chemical pDepot (NECD)
Information
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History 1941 Est. Wabash River Ordnance Works
1943-46 Manufacture RDX Explosives
y
1943-44 Constructed Facility For Heavy Water
1944-46 Heavy Water Productiony
1951-57 Manufacture RDX Explosive
1952-57 Heavy Water Production
1958-61 Built VX Facility
1961-68 Manufactured Chemical Agent VX
i d i 1969 Moratorium on VX Production & Shipment
1968-73 Construction of TNT Facility
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1973-74 TNT Production
1993 Lost TNT Mobilization Mission
NECD Mission
Safe and Secure Storage of Agent VXg
Environmental Compliance & Stewardship
Chemical Treaty Compliance Program
Chemical Stockpile Disposal ProgramProgram
Chemical Stockpile Emergency Preparedness Program
Train Soldiers
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Maintain Plant Facilities
NECD Features
7,097 Acres – 4,000 Leased for Agriculture g– 1,900 Standing Timber– Wildlife
Security/Fire yDepartment
3 Installation Wells -- 7 Mil Gal ReservoirMil. Gal. Reservoir
Sewage Treatment Plant (3,000 pop.)
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Personnel GOCO - Government Owned, Contractor Operated
– Mason & Hanger Corporation, (Day & Zimmermann)Mason & Hanger Corporation, (Day & Zimmermann) Philadelphia, PA.• Fourth-largest Employer in Vermillion County• Operating Contractor Since 1986Operating Contractor Since 1986
Gov’t Staff - 2 Military, 13 DoD Civilians1 IMA– 1 IMA,
– Additional Population:• Newport Chemical Agent Disposal Facility• Chemical Stockpile Defense Force (CSDF)• Chemical Stockpile Defense Force (CSDF)• Tennessee Valley Authority• SAIC
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Non-Stockpilep
Demolition of the Former VXProduction Facility
Step IIIAugust 2000 - 2007Steps 0,I,II
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p , ,Completed 2002
Newport Community Outreachp y
••Location in Newport CommunityLocation in Newport Community••Integrated NECD/NECDFIntegrated NECD/NECDFOutreach Strategy Outreach Strategy gygy••Speakers’ BureauSpeakers’ Bureau••School ProgramsSchool Programs••Public Availability SessionsPublic Availability Sessions••Public Availability SessionsPublic Availability Sessions••Information RepositoriesInformation Repositories••Information Exchange With Information Exchange With E i D l A iE i D l A iEconomic Development AgenciesEconomic Development Agencies••Presence at Fairs, Festivals and Presence at Fairs, Festivals and ExhibitsExhibits
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NECDF HistoryNECDF History
1997 A l d l i h l 1997 – Approval to demonstrate alternative technology –caustic neutralization
1999 – Design/Build/Operate Contract awarded to Parsons1999 Design/Build/Operate Contract awarded to Parsons (Parsons partners include Alion for laboratory operations and Perma-Fix for hydrolysate disposal)
2000 – Construction begins Terrorist attacks of September 11, 2001
11 M 2002 A i iti D i i M d (ADM) 11 May 2002 – Acquisition Decision Memorandum (ADM) signed authorizing the accelerated destruction of the stockpile
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p
VX N A tVX Nerve Agent InformationInformation
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Nerve Agent Historyg yMost nerve agents belong to a group of chemicals called "organophosphates". The first of these chemicals was made in 1854 and was originally developed to be
d l i d Th fi ( ll d "T b "used to control insects and save crops. The first nerve agent (called "Tabun" or "GA") for military use was made in Germany in 1936. Another nerve agent, "sarin" or "GB," was made in 1938 and "Soman" or "GD" was made in 1944. It appears that these nerve agents were not used by the Germans during World Warappears that these nerve agents were not used by the Germans during World War II. However, it has been estimated that the Germans had stockpiles of tons of both Tabun and Sarin. The United States and Russia continued producing and stockpiling these nerve agents after the War In the 1950's another nerve agentstockpiling these nerve agents after the War. In the 1950 s another nerve agent, "VX", was produced in England.
First Made Lethal Dose Lethal Dose(Year) Breathing (mg*min/m3) Skin (mg)Name (Year) Breathing (mg min/m ) Skin (mg)
Tabun (GA) 1936 150-400 1,000-1,700
Sarin (GB) 1938 75-100 1,000-1,700Soman
Name
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Soman (GD) 1944 35-50 50-100
VX 1952 10 6-10
There are several less common nerve agents: GE, GF, VE, VG and VM
VXCAS REGISTRY NUMBERS: 50782-69-9, 51848-47-6, 53800-40-1, 70938-84-0
CHEMICAL NAME: O-ethyl-S-(2-iisopropylaminoethyl) methyl phosphonothiolate
TRADE NAME AND SYNONYMS:Phosphonothioic acid, methyl-, S-(2-bis(1-methylethylamino)ethyl) o-ethyl ester O-ethyl S-(2-diisopropylaminoethyl) methylphosphonothiolate S-2-Diisopropylaminoethyl O-ethyl methylphosphonothioate S-2((2-Diisopropylamino)ethyl) O-ethyl methylphosphonothiolate O-ethyl S-(2-diisopropylaminoethyl) methylphosphonothioate O-ethyl S-(2-diisopropylaminoethyl) methylthiolphosphonoate S-(2-diisopropylaminoethyl) o-ethyl methyl phosphonothiolate Ethyl-S-dimethylaminoethyl methylphosphonothiolate y y y y p pVX EA 1701 TX60
MOLECULAR WEIGHT: 267.38
CHEMICAL FAMILY: Sulfonated organophosphorous compound
FORMULA / CHEMICAL STRUCTURE: C11H26NO2PS / CH3PO(OCH2CH3)S(CH2)2N(CH(CH3)2)2
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VXPhysical and Chemical Properties Physical State:
Liquid BOILING POINT : 298 C (568 F) VAPOR PRESSURE (mm Hg): 0 0007 @ 20 CVAPOR PRESSURE (mm Hg): 0.0007 @ 20 C VAPOR DENSITY (AIR=1): 9.2 FREEZING/MELTING POINT : Below -51 C LIQUID DENSITY (g/cc): 1.0083 @ 20 C PERCENTAGE VOLATILE BY VOLUME: 10.5 mg/m3 @ 25 C SOLUBILITY: Slightly soluble in water at room temperature. Soluble in organic solvents.APPEARANCE AND ODOR: Colorless to straw colored liquid & odorless, similar in appearance to
motor oil.FLASHPOINT: 159 C (McCutchan - Young)
VX agent is one of the most dangerous chemicals created. It is used in chemical warfare. In the film "The Rock", it was that green liquid that the terrorists threatened San Francisco Bay with.
VX agent was developed in the Porton Down Chemical Weapons Research Centre, Wiltshire, England in 1952 and its
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devastating effects were tested. The British traded the technology of VX with the United States of America for information on thermonuclear weapons.
How VX works
Nerve agents renders the enzyme cholinesterase inactive. This allows thecholinesterase inactive. This allows the neurotransmitter acetylcholine to buildup in the body.
Acetylcholine is produced by the body and functions as a transmitter.
Nerve agents interfere with the signaling system used by the nervous system.
Many organophosphates inhibit acetylcholinesterase, an essential chemical that breaks down the neurotransmitter acetylcholine whichneurotransmitter acetylcholine, which carries nerve signals across gaps between nerve cells.
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Source: A FOA Briefing Book on Chemical Weapons: Nerve Agents
Signs and Symptoms for VXg y p Dose / Duration and Route of exposure make a difference
V E (li ht / i iti l) Vapor Exposure (light / initial)– Miosis– Dimming of vision– Lacrimation – excessive tear formationLacrimation excessive tear formation– Rhinorrhea – excessive runny nose– Tightness in chest
Vapor Exposure ( High Concentration )Vapor Exposure ( High Concentration )– Drooling– Coughing– Sweating
Abdominal Cramping
– Uncontrolled diarrhea– Urination– Seizures
Convulsions– Abdominal Cramping– Vomiting– Uncontrolled diarrhea– Urination
– Convulsions– Loss of consciousness– Respiratory failure– Death
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Signs and Symptoms for VX( ti d)(continued)
Skin Exposure (Percantaneous)– Redness of areaed ess o a ea– Muscle Twitching– Muscle Spasms– Generalized weakness
Ingestion (Gastrointestinal)– Look for later signs and symptoms of High vapor exposure– Signs and symptoms for ingested VX may take several hours to display
Nerve Agent Antidote– Atropine (administered to block receptor sites of acetylcholine)– 2-PAM Chloride (restores acetylcholinesterase)
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Chemical Agent VXProd ction
Four step process
Production
manufactured in campaigns (step 0 I II and III)0,I,II,and III)
• Process Steps 0 - II Produced precursorProduced precursor chemical used in Step III
• Process Step III produced chemical warfare agent VX
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warfare agent VX
Accelerated Ton Container Destruction
• Drain containers manually using glove box system
i d i d i• Rinse drained containers, return to appropriate storage
• Neutralize agent in reactorNeutralize agent in reactor vessels
• Ship neutralized by-product (hydrolysate) to off-site commercial treatment facility
• After agent neutralization, complete decontamination of containers and recycle
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and recycle
Neutralization Process
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Governing Requirements
Source RequirementSource Requirement
Chemical Weapons Convention Irreversible Destruction of Schedule 1 Compounds (i.e., VX and EA2192)
Federal Statute Clean Water Act - No Release of Agent
EPA G id MDL (40 CFR P t 136 A di B)EPA Guidance MDL (40 CFR Part 136 Appendix B)
Indiana Statute Six-Nine Destruction, Low Temperature, Low Pressure, Comparable Facility
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“Neutralization”Neutralization Neutralization is a term used by the ChemicalNeutralization is a term used by the Chemical
Demililitarization community indicating that the effects of chemical weapons have been removed (i.e., VX nerve
ff di h VX i li d)agent effects disappear when VX is neutralized)– NOTE: In the Chemistry Community Neutralization only
refers to pH conditions. Water (H2O) is neutral (pH 7). p ( 2 ) (p )A basic solution (pH > 7) can be neutralized to pH 7 by adding acid.
VX can be “neutralized” in several ways. Those tested by the Army include water, Caustic, and Bleach– Caustic Neutralized VX Hydrolysate is approximately
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Caustic Neutralized VX Hydrolysate is approximately 10,000 times less toxic than VX
VX “Neutralization”VX Neutralization VX “Neutralization” using water or caustic is a g
Hydrolysis Reaction– “Hydro” from Water indicates adding a water molecule to
VXVX– The NECDF process uses Caustic because it effectively
destroys both VX and EA 2192
Caustic Hydrolysis reactions are also called “Saponification” Reactions (see next slide for example p ( f pof this reaction type)– The 5000 year-old process of making soap is a classic
“saponofication” reaction
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saponofication reaction
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NECDF ProcessNECDF Process VX added to hot caustic (194ºF, 20.4 wt.% NaOH)
72 min te feed time ( 5 gpm)– 72 minute feed time (~ 5 gpm)– VX neutralization is “exothermic” [it gives off heat] – slow agent feed minimizes temperature variations – Reactor contents stirred at temperature for 2.5 hours under
Nitrogen (N2) blanket
R l d 100°F d l d Reactors are cooled to 100°F and sampled– 2 samples will be taken from each batch
H d l t i t f d t h ldi t k ithi Hydrolysate is transferred to holding tanks within the reaction area until cleared.
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Why’s and What’sWhy s and What s
Why is temperature so important?Why is temperature so important?– Temperature affects the speed of reactions. VX reacts
117 times faster at 194ºF than at 77ºF !Wh thi t t h t it b d– When things get too hot it can be dangerous
• Volatilization rates increase with temperature• Pressure increases (Pressure release valve will open)( p )• Unexpected thermal decomposition products
Why is mixing so important?– VX is insoluble (i.e., doesn’t dissolve) in caustic– In order to react, VX and OH- have to come in contact so
there has to be good mixing !
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there has to be good mixing !
More Why’s and What’sMore Why s and What s
f f if * f i i i 1 2If the half-life* of VX in caustic is 1 – 2 seconds, why do we let it react for 2.5 hours?– We want to make sure we get all the VX !We want to make sure we get all the VX !– VX isn’t the only thing we have to get rid of… EA 2192
must be below 20 ppm before hydrolysate leaves the t b ildireactor building.
• The half-life for EA 2192 is about 10 minutes!!• EA 2192 also serves as a process Performance Indicator p
(PI) - if after the 2.5 hours, EA 2192 is still there (above 20 ppm) the reactor mixing isn’t enough to ensure fast VX reaction
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ensure fast VX reaction
VX Caustic Neutralization
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VX ReactionVX Reaction
Th h lf lif f VX i 20 4% ti t 194°F i The half-life of VX in 20.4% caustic at 194°F is between 1 and 2 seconds – therefore by the end of fill, most of the VX will be gone!of fill, most of the VX will be gone!
The half-life of EA 2192 in 20 4% caustic atThe half-life of EA 2192 in 20.4% caustic at 194°F is estimated to be on the order of 10 minutes. In order to pass hydrolysate clearance criteria, EA 2192 must be below 20 ppm in the hydrolysate (a process control criteria).
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VX Neutralization ProcessWater & Water & CausticCaustic
Ton ContainerTon Container NitrogenNitrogen
Chemical Agent Chemical Agent Transfer SystemTransfer System ReactorReactor
HydrolysateHydrolysate
Agent Agent Holding Holding
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TankTank
History of Low Level VX Analysis of HydrolysateAnalysis of Hydrolysate
(1994 - 2000)
Scale Method Detection LimitsLaboratory Glass NMR 1 20yReactor < 2 Liters
NMR 1 - 20 ppm
Bench - 2 Liters
Mettler HPLC-MS-MS 100 ppbMettler Calorimeter
HPLC MS MS 100 ppb
Bench - 114 L Reactor
Chloroform Extraction 80 200 b DLeacto
- 12 L Mettlert act o
GC-ITMS 80-200 ppb DL
CAMDS - 100 Gallon Reactor
Hexane - Acid Hexane and C2 MDL Less Than 20 ppb
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00 Gallon Reactor ess a 0 ppb
Genesis of Project Speedy Neutralization
Adjunct to additional security measures adopted by the Army following the September 11, 2001, terrorist
tt kattacks– On-site relocation of stockpile– Deployment of National Guard soldiersp y
Goal is to accelerate the disposal of bulk agents– Mustard (HD) at Aberdeen Proving Ground, MD – VX nerve agent at Newport Chemical Depot, IN
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What exactly is Hydrolysate
“Hydrolysate” is just the name give to the mixture that results from the caustic hydrolysis of VX
It’s major constituents correspond to the breakdown d t f VX d id l tiproducts of VX and residual caustic:
– Thiolamine, EMPA, MPA, NaOH, ureas– NOTE: Because of the residual NaOH (~ 3.7 wt%), f ( )
hydrolysate is very CORROSIVE! The thiolamine is oxidized by air and makes a disulfide
that floats on top of the caustic along with the ureas, and other organics– The flash point of the upper organic layer is 127ºF
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The flash point of the upper organic layer is 127 F
P t ti U d tProtection Used to Ensure SafetyEnsure Safety
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Classification of HVAC AreasClassification of HVAC Areas
Category A—toxic process area under negative pressure possible contamination with liquid agent.C t B t i d ti Category B—toxic process area under negative pressure possible contamination with vapor.
Category C—negative pressure subject to vapor Category C—negative pressure subject to vapor contamination.
Category D—ambient air pressure, not contaminated.g y p , Category E—area with filtered air, positive pressure
atmospheres.
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VX Air Filtration SystemVX Air Filtration System
P rocess U nder N orm al O perationParticulate Pre-filter H EPA
Six active carbon filter
banks H E PAPre-filter L P r � C
4 A
4 0 i P r eP S n e
A S n e
C n i P 2
r t e4 A
A S n e – t r S t n S r D e l � q S b 2 i r
– t r S t n S r D e � e A 0 P n 2 C e– t r S t n S r D e � e A 0 P n 2 C
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30
12/6/2002 47
Decontamination Levels -E i tEquipment
1 X – Item may have been decontaminated but it still has agent presentit still has agent present.
3X – Item has been surfaced deconned bysurfaced deconned by approved procedures.
5X – Item deconned and can be sold to the public.
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Safeguarding PersonnelSafeguarding Personnel
All personnel entering the Limited Area will be issued M40-series mask and 3 Mark 1 Kits
All clothing will be changed at the beginning g g g gand end of the work shift for all agent workers that will enter the Exclusion Area.
Eating, drinking, chewing and smoking within the Limited Area is prohibited unless specifically approved
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specifically approved.
Personnel Protective Clothing L l ALevel Ata
ry
HA
Mili
t
OSH
M
Demilitarization Personnel Ensemble Military attire for chemical agent
work
Highest level of protection
High potential for splash or t ki h d
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work. Provides the most protection against
chemical or biological hazards.
exposure to skin hazards
IDLH or unknown environment
Personnel Protective Clothing L l BLevel Bta
ry
HA
Mili
t
OSH
Provide the next best protection against chemicals
Highest level of respiratory and some degree of skin protection
P f
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Presence of vapor or gas
Direct contact with contaminant unlikely
Personnel Protective Clothing L l CLevel Cta
ry
HA
Mili
t
OSH
Level C Protective Clothing Next best protection against chemical Uses the M40 mask
Used when contaminant is known
Level of contaminant is measured
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Uses the M40 mask Criteria for wearing APR is met
Severe skin hazard unlikely
Personnel Protective Clothing L l DLevel Dta
ry
HA
Mili
t
OSH
Level D Protective Clothing Least amount of protection against
chemical
Minimal protection from physical hazards
Hazardous free atmosphere
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Uses the M40 respirator slungHazardous free atmosphere
Work precludes potential for exposure to hazardous substances
Personnel Protective Clothing L l D Oth V i tiLevel D – Other Variations
Also Class D protective clothing M40 respirator slung Least protection against chemicals
Also Class D protective clothing M40 respirator slung
T i ll b i it t i t
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Least protection against chemicals Primarily used in laboratory
situations
Typically worn by visitor, transient workers, or non-agent workers.
Monitoring Methods
Two methods will be utilized in the VX air monitoring system
A l ti it i t i i– A near real-time monitoring system is primary analytical method used for all workplaces (MINICAMS)(MINICAMS)
– DAAMS a manual method used for integrated air sampling and confirmation analysis.p g y
Sulfur monitors will be used for Hydrolosate
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Air Monitoring Concept
MINICAMS DAAMS
Outside and Inside the Work Area Structure (Secondary Containment)
Support NRT monitoringStructure (Secondary Containment)
– Utilize MINICAMS cycling every 380 seconds (180 sampling/200 analysis).
– MINICAMS alarm will be generated on a response ≥0.7 TWA.
Confirmation DAAMS sampling will be initiated on MINICAMS work area alarms.C fi ti DAAMS ill b l d
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a response ≥0.7 TWA. Inside the Primary Containment on
individual sample basis, not continually.
Confirmation DAAMS will be sampled to obtain a 12L sample.
H b d ’ P j tHaraburda’s ProjectLeadership RulesLeadership Rules
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Haraburda’s ProjectL d hi R lLeadership Rules
Projecto Cannot have all three: cheaper, better, faster.
Communicationo Consensus usually results in “weakest
d i ” d i io Accomplishing the task is more important than the tool used.
o Plan and sacrifice now for the sake of the future.o A poor plan implemented is much better than the best
plan that is not implemented
denominator” decisions.o Meetings should be short, infrequent, and value-
added.o Communicate the results, both the good with the
bad.plan that is not implemented.
DataM i h ld b d if l i (f
o Sell the good statements, not the bad, even though it is easier for the bad ones.
Problem Solvingo Toda ’s problems come from esterda ’so Metrics should be used if one plans to use it (for
decisions).o Understand the source of the data.o Meaningless goals, even if easily obtained, should not
be used.
o Today’s problems come from yesterday’s solutions.
o The cure can be worse than the disease.o Dominate technology – do not let it dominate
you.o Challenge Your Assumptions (CYA).
Peopleo A project begins, ends, sinks, and swims with people.o Reward good performers; coach or remove bad ones
o Solve the problems, not the symptoms.
Decision-Makingo Doing the right thing is better than doing things
right
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o Reward good performers; coach or remove bad ones.o Train your successor.o Do not try to please everyone, someone will not like it.
right.o Better is the enemy of “good enough.”o Resources mean nothing if not used.o If it “ain’t broke,” either maintain or improve it.
Q ti ????Questions ????
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R A P H YI O GB R A P H YI O GBSCOTT S. HARABURDA, PhD, PE
Lieutenant Colonel, US Army
Lieutenant Colonel Scott S. Haraburda has given over twenty-two years to thepeople of the United States as both an Officer and an Enlisted Soldier in theUnited States Army. As an army reserve officer, he is currently the commanderof the 472nd Chemical Battalion. His other reserve assignments includeengineering and contingency contracting positions within 8th US Army, researchand development positions for Army Material Command, and admission related
iti f th U it d St t Milit A d t W t P i t Li t tpositions for the United States Military Academy at West Point. LieutenantColonel Haraburda served on active duty for 9 years, with assignments inadvising about chemical warfare at Fort Hood, Texas and teaching chemistry atWest Point, New York. In 1991, Lieutenant Colonel Haraburda was one of threeofficers nominated by the Army to become an Astronaut Candidate for NASA.
In addition to being both a branch qualified chemical and engineer officer,Lieutenant Colonel Haraburda is a member of the Army Acquisition Corps
He earned a BS in chemistry in 1983 from Central Michigan University(CMU), a MS in chemical engineering in 1990 and a PhD in chemicalengineering in 2001 from Michigan State University (MSU). As aDistinguished Military Graduate of the ROTC program at CMU he receivedLieutenant Colonel Haraburda is a member of the Army Acquisition Corps
(AAC). As part of his training within the AAC, he has completed several dozencourses from the Defense Acquisition University. With his training andexperience in the acquisition field, Lieutenant Colonel Haraburda hascertifications in the following fields: 1) Program Management; 2) Contracting; 3)Systems Planning, Research, Development and Engineering; 4) InformationTechnology; and 5) Test & Evaluation Engineering. Additionally, he successfullycompleted the Department of Defense Chief Information Officer Certificate
Distinguished Military Graduate of the ROTC program at CMU, he receivedhis commission as an army officer in 1983. He is also a graduate of theChemical Officer Basic and Advanced Courses, the Engineer Captains CareerCourse, the Combined Arms Services Staff School, the Associate LogisticsExecutive Officers Course, the US Army Command and General Staff College,the US Naval Command and Staff College, the Defense Strategy Course at theUS Army War College, and the US Air War College.
p pprogram from the Information Resource Management College.
In his civilian life, Dr. Haraburda worked at Bayer Corporation for 4 years inPennsylvania and West Virginia, as a process engineer. In addition to Bayer, heworked at G.E. Plastics for 4 years as a production engineer in Mount Vernon,Indiana. Since June 2000, Dr. Haraburda has been working as a civilian for theUS Army as the assistant project manager for the Newport Chemical AgentDisposal Facility in Indiana where several tons of VX nerve agent will be
For his exemplary accomplishments and dedication, Lieutenant ColonelHaraburda has received the Army Commendation Medal with three Oak LeafClusters, Army Achievement Medal with three Oak Leaf Clusters, ArmyReserve Component Achievement Medal with two Oak Leaf Clusters, NationalDefense Service Medal, Armed Forces Reserve Medal with Bronze Hourglass,Army Service Ribbon, Army Reserve Components Overseas Training Ribbonwith Numeral Three, Air Assault Badge, and German Armed ForcesP fi i B d i B
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Disposal Facility in Indiana where several tons of VX nerve-agent will bedestroyed. He is a registered Professional Engineer (PE) in the State of Indiana.Dr. Haraburda wrote 11 technical articles, wrote 6 management articles, wrote 1chemical engineering handbook, and presented 7 international electric propulsionconference articles. He has also filed 10 patent applications.
Proficiency Badge in Bronze.