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Chapter 16
TERRORISM, TOXICITY, AND VULNERABILITY: GREEN
CHEMISTRY AND TECHNOLOGY IN DEFENSE OF
HUMAN WELFARE
Green Chemistry and the Ten Commandments of
Sustainability, 3rd Edition
Stanley E. Manahan
ChemChar
(Amazon/CreateSpace)
2011
For questions, contact:
Stanley E. Manahan
manahans@missouri.edu
Prepared for Macintosh OS-X
May require some reformatting for PC
16.1.VULNERABILITYTOTERRORISTATTACK
Chemicalsharmingpeopleinterroristattacksandaccidents
Explosivemixtureofammoniumnitrate(acommonagricultural
fertilizer)anddieselintheattackontheAlfredP.Murrah
OklahomaCityFederalBuildingin1995
ExplosivesusedbysuicidebombersintheMiddleEast
MethylisocyanateintheindustrialchemicalaccidentinBhopal,
India,in1984
Almost200killedbyhydrogensulfideinnaturalgasreleased
ChuandongbeinaturalgasfieldofsouthwesternChinain
December,2003
Environmentsusceptibletoterroristattack
16.2.PROTECTINGTHEANTHROSPHERE
Infrastructure
Waterpurificationanddelivery
Electricitygenerationanddistribution
Transportationinfrastructure
Vulnerabilityduetointerconnectivity
Failureofelectricalgrids
Cascadingfailuresoncomplexnetworksthatoperateclosetothe
edgesothatarelativelysmallfailurecanrapidlycascadeintoa
majorfailure
ElectricalgridsInternetsystemsJustintimemanufacturing
Chemistrycanbeappliedtoinfrastructureprotection
Example:Productionofmaterialsthatresistheatandflame
16.3.SUBSTANCESTHATEXPLODE,BURN,ORREACT
VIOLENTLY
Explosives
16.4.TOXICSUBSTANCESANDTOXICOLOGY
Table16.1.MajorTargetSystemsofToxicSubstances
Targetsystem
Typicaltoxicresponses
Respiratorysystem
Emphysemafromcigarettesmoke,lungcancer
fromasbestos
Allergiccontactdermatitis,suchasfromexposure
todichromate;chloracnefromexposureto2,3,7,8
tetrachlorodibenzopdioxin(dioxin);skincancer
fromexposuretocoaltarconstituents
Steatosis(fattyliver),suchasfromexposureto
carbontetrachloridecirrhosis;(depositionand
buildupoffibrouscollagentissue)fromexcessive
ingestionofethanol;haemangiosarcoma,atypeof
livercancerobservedinworkersheavilyexposedto
vinylchlorideinPVCplasticmanufacture
Interferencewithspermdevelopmentbysome
industrialchemicals,interferencewithcells
involvedwitheggformationbychemicalssuchas
cyclophosphamide
Skinresponses
Hepatotoxicity(toxic
effects)
Reproductivesystem
Table16.1.MajorTargetSystemsofToxicSubstances(Cont.)
Blood
Immunesystemeffects
Endocrinesystemeffects
Nervoussystem
Kidneyandurinarytract
system
Carboxyhemoglobinformationfrombindingof
carbonmonoxidetobloodhemoglobin,
methemoglobinemiaconsistingofconversionof
iron(II)toiron(III)inhemoglobinfromexposureto
substancessuchasanilineornitrobenzene,aplastic
anemiafromexposuretobenzene
Immunosuppressionfromexposuretoradiation,
hypersensitivityfromexposuretoberyllium
Disruptionofendocrinefunctionbyendocrine
disruptorssuchasbisphenolA
Encephelopathy(braindisorder),suchasfrom
exposuretolead;peripheralneuropathyfrom
exposuretoorganicsolvents;inhibitionof
acetylcholinesteraseenzymeinnervefunctionby
exposuretoorganophosphatemilitarypoisons
Nephrotoxicitytothekidneybyheavymetal
cadmium
Relative Toxicities
*LD50valuesareinunitsofmgoftoxicantperkgofbodymass.
# Pufferfishtoxin
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RelativeToxicitiesofInsecticidalParathionandNerveGasSarin
MetabolismofToxicSubstances
Xenobioticsubstancesarethosethatarenormallyforeigntoliving
systems
Xenobioticsubstances,aresubjecttometabolicprocesses
Activatetomoretoxicsubstance
Converttolesstoxicsubstance(detoxication)
Twophasesofmetabolismoftoxicsubstances
PhaseIreactionsnormallyconsistofattachmentofafunctional
group,usuallyaccompaniedbyoxidation
PhaseIIreactionsconsistofbindingtoanendogenousconjugating
agent,typicallyglucuronide
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Phase I Reactions
Phase II Reactions
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16.5.TOXICCHEMICALATTACK
Bhopal
Accidentalreleaseofmethylisocyanatefromachemical
manufacturingoperationinBhopal,India,duringthenightof
December2/3,1984illustratespotentialforterroristattack
About40tonsofmethylisocyanatewasreleasedexposing
thousands
Morethan3000died,primarilyfrompulmonaryedema(fluid
accumulationinthelung)
Immunological,neurological,ophthalmic(eye),andhematological
effects
Methylisocyanateisthemosttoxicoftheisocyanates
HighvaporpressureToxicitytomultipleorgans
CrosscellmembranesReachorgansfarfromexposuresite
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Carbonmonoxidebindingwithhemoglobin:
O2Hb+COCOHb+O2(13.5.1)
Effects
10ppm:Impairedvisualperceptionandjudgment
100ppm:Dizziness,headache,andfatigue
250ppm:Unconsciousness
1000ppm:Rapiddeath
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MilitaryPoisons
Mustardoil,bis(2chloroethyl)sulfide:
Vaporspenetraterapidlyanddeeplyintotissue
Tissuedamageanddestructionwellbelowthepointofentry
Blisteringgasproducingseverelyinflamedlesionsthatare
susceptibletoinfection
Likelytobefatalinlungs
Mutagenandpossiblecarcinogen
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Nerve Gases
Nervegasorganophosphatesarethemilitarypoisonsofmostconcern
Sarin
Tokyosubwayattack
Fatalatadoseofonlyabout0.01milligramsofSarinperkilogram
ofbodymass
Singledropthroughtheskincankillahuman
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Ricin Biotoxin
Ricin
Verystableproteinaceousmaterialextractedfromcastorbeans
(Ricinuscommunis)
Injectionofanamountaboutthesizeofapinheadcanbefatal
Failureofkidneys,liver,andspleenalongwithmassivebloodloss
fromthedigestivetract
Hazardlessenedbyneedtoinject
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16.6.PROTECTINGWATER,FOOD,ANDAIR
Chemicalattackonfoodsupplyatasufficientscaletocausemany
poisoningsisnotlikely
Attackonfoodsupplybymicroorganisms
Anthraxbacteriathroughairorcontact,suchasthroughmail
Shigelladysenteriaebacteriaonfoodcancauseseveredysentery
Salmonellabacteriaincontaminatedfoodcancausedebilitating
digestivetracteffects
Althoughusuallynotfatal,Salmonellaonfoodhavethepotential
tocausetemporarydisability
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16.7.DETECTINGHAZARDS
Explosives
ResiduesofTNT,RDX,andPETNexplosivesdetectedby
sophisticatedinstrumentsincludingionmobilityspectrometersand
chemiluminecencesensors
Nuclearquadrupoleresonance(NQR)maybeusefultodetect
explosivesbecauseitrespondstonitrogen,whichallmajor
explosivescontain
Canineolfactorydetection(dogsnose)
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16.8.GREENCHEMISTRYTOCOMBATTERRORISM
Safeandsustainablegreenchemistrycanhelpcombatterrorism
Hazardoussubstancesthatmightbestolenordivertedforusein
attacksarenotmadeorusedinlargequantities
Chemicalproductsdowhattheyaresupposedtodoandareusedin
minimumquantities
Materialsandprocessesthatarelikelytoresultinviolentreactions,
fires,highpressures,andotherextremeconditionsareavoided
Potentiallyhazardousauxiliarysubstancesandflammable
materialsareavoided
Minimizesenergyconsumption,therebyreducingenergetic,high
temperatureprocessesthatmightbesusceptibletosabotage
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16.9.GREENCHEMISTRYFORSUSTAINABLE
PROSPERITYANDASAFERWORLD
Reducingpoverty,humanmisery,andhopelessnesshelpsalleviate
conditionsthatpromoteterrorism
Peoplewithsatisfiedmaterialneedsabletoleadcomfortableand
fulfillinglivesarerelativelylesslikelytocommitviolentacts
Greenchemistryfulfillshumanneedsandmakeslifemore
comfortable
Prosperity,narrowlydefined,hasresultedinconsumptionof
increasinglyscarceresourcesandenvironmentaldegradation
Quote:Wearepastthedayswhenwecantradeenvironmental
contaminationforeconomicprosperity;thatisonlyatemporary
bargain,andthecostofpollutionbotheconomicallyandonhuman
healthistoohigh.
Greenchemistryandthepracticeofindustrialecologycanprovide
highlivingstandardssustainably
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Energy (Cont.)
Problemswithenergy
Energysourcestendtobecontentiousandcompetitionforthem
hasprecipitatedpastwars
Somemajorregionsofpetroleumofpetroleumproductionare
breedinggroundsforterrorists.Theprovisionofadequateenergy
independentofsuchsourceswouldsubstantiallyreduceterrorist
threats.
Abundant,sustainableenergycanleadtolessterrorpronesocieties
Productionoffoodthroughsynthesisoffertilizers(particularlyby
syntheticfixationofatmosphericnitrogen)andforirrigation,
cultivation,andreclamationoffarmland
Fabricatematerialsforhousingandprovidetheheating,cooling,
andlightingrequiredtomakedwellingscomfortable
Pumpwaterfromabundantsourcestomorearidregions
Purifymarginalsourcesofwaterandreclaimwaterafteruse
Desalinatewater
Providesafe,comfortable,nonpollutingtransportationsystems
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Energy (Cont.)
Abundant,sustainableenergyrequiresthebestpracticeofgreen
chemistry,greenengineering,andindustrialecology
Increasedefficiencyofenergyutilizationisakeyaspectof
providingmoreusableenergy
Solar,wind,andbiomassenergyaresustainable,renewableenergy
sources
Fossilfuelswillplayaninterimrole,especiallyifsequestrationof
greenhousegascarbondioxidebyproductcanbeachieved
Nuclearfissionwithuraniumfuelcanprovideabundantenergy
safelywithnewgenerationnuclearreactorsandreprocessingof
nuclearfuel.
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Energy (Cont.)
Becausewindandsolarsourcesarebynatureintermittentand
dispersedandoftenproduceelectricityinlocationsfarfromwhereit
isused,storageandtransportofenergyareveryimportant
Superconductororquantumconductorpowercablesarecandidates
fortransportofelectricalenergyfromsourcetouse
Pumpedwaterhydroelectricstorageorhighspeedflywheels
coupledwithelectricmotor/generators
Elementalhydrogen,H2,willbewidelyusedforenergystorage
andtransportaswellasforfuel,movedbypipelineandusedto
produceelectricitydirectlyinfuelcells
Hydrogenfromelectrolysisofwater
Directphotoconversionofwatertohydrogenandoxygenmay
eventuallybecomepractical
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