1

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
[email protected]
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

Protection With Green Chemistry

Greenchemistrytomitigateterroristthreats
Usesthesafestpossiblechemicalsassafelyaspossible
Minimizestheaccumulationofhazardouschemicalsand
eliminateshazardouschemicalwastes
Betterdetectionofhazardousmaterials
Effectivesubstitutematerialstoreducepotentialforresource
blackmail
Sustainableenergysourcestoreduceenergyblackmailsuchas
suppliesofpetroleumandnaturalgas
BiochemistryandrecombinantDNAsciencetoenablethe
developmentofbettervaccinesagainstpathogenicbiological
warfareagentsandantidotestochemicalandbiologicaltoxins

16.2.PROTECTINGTHEANTHROSPHERE
Infrastructure
Waterpurificationanddelivery
Electricitygenerationanddistribution
Transportationinfrastructure
Vulnerabilityduetointerconnectivity
Failureofelectricalgrids
Cascadingfailuresoncomplexnetworksthatoperateclosetothe
edgesothatarelativelysmallfailurecanrapidlycascadeintoa
majorfailure
ElectricalgridsInternetsystemsJustintimemanufacturing
Chemistrycanbeappliedtoinfrastructureprotection
Example:Productionofmaterialsthatresistheatandflame

16.3.SUBSTANCESTHATEXPLODE,BURN,ORREACT
VIOLENTLY
Explosives

Hazardous Substances (Cont.)

Flammablefuelsandsolvents
Corrosivesubstances
Sulfuricacid
Hazardoussubstanceswidelyusedinindustry
Practiceofindustrialecologyandgreenchemistryminimizes
threats,producingandusinghazardoussubstances
Inminimalquantities
Whereneeded
Asneeded,justintime

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

10

RelativeToxicitiesofInsecticidalParathionandNerveGasSarin

MetabolismofToxicSubstances
Xenobioticsubstancesarethosethatarenormallyforeigntoliving
systems
Xenobioticsubstances,aresubjecttometabolicprocesses
Activatetomoretoxicsubstance
Converttolesstoxicsubstance(detoxication)
Twophasesofmetabolismoftoxicsubstances
PhaseIreactionsnormallyconsistofattachmentofafunctional
group,usuallyaccompaniedbyoxidation
PhaseIIreactionsconsistofbindingtoanendogenousconjugating
agent,typicallyglucuronide

11

12

Phase I Reactions

Most Phase I reactions are microsomal mixed-function oxidase

Reactions
Catalyzed by the cytochrome P-450 enzyme system
Associated with cell endoplasmic reticulum
Occurring most abundantly in the liver of vertebrates

Phase II Reactions

13

Phase I and Phase II Reactions and Toxicity

Insomecases,PhaseIandPhaseIIreactionsmakesubstancestoxic
ormoretoxic
Mosthumancarcinogensareproducedmetabolicallyfromnon
carcinogenicprecursors

14

Dynamic Phase of Toxicity

15

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

16

Potential Chemical Agents

Carbonmonoxide
Haskilledthousandsaccidentallyandbysuicide
Odorless,nowarning

Carbonmonoxidebindingwithhemoglobin:
O2Hb+COCOHb+O2(13.5.1)
Effects
10ppm:Impairedvisualperceptionandjudgment
100ppm:Dizziness,headache,andfatigue
250ppm:Unconsciousness
1000ppm:Rapiddeath

17

Potential Terrorist Agents (Cont.)

Chlorine(Cl2)
Widelyused
FirstmilitarypoisoninWorldWarI
Strongoxidizerthatformsacidsandisespeciallydamagingto
respiratorytissue
1020ppm:Acuterespiratorytractdiscomfort
1000ppm:Rapidlyfatal
Hydrogencyanide,HCN,isahighlytoxicgaseoussubstancewith
potentialforattackthroughtheatmosphere
Alsotoxicassalts,suchasKCN(potentialattackthroughfoodand
water)
Cyanidebindswithironinthe+3oxidationstateofferricytochrome
oxidaseenzymepreventingutilizationofO2leadingtorapiddeath
Antidoteistoformironinthe+3oxidationstatefromblood
hemoglobintoproducemethemoglobinthatbindswithcyanide

18

Potential Terrorist Agents (Cont.)

Hydrogensulfide,H2S
Colorlessgaswithafoul,rotteneggodor
Astoxicashydrogencyanideandmaykillevenmorerapidly
1000ppm:Rapiddeathfromrespiratorysystemparalysis
Nonfataldosescancauseexcitementduetodamagetothecentral
nervoussystem;headacheanddizzinessmaybesymptomsof
exposure

19

MilitaryPoisons
Mustardoil,bis(2chloroethyl)sulfide:

Vaporspenetraterapidlyanddeeplyintotissue
Tissuedamageanddestructionwellbelowthepointofentry
Blisteringgasproducingseverelyinflamedlesionsthatare
susceptibletoinfection
Likelytobefatalinlungs
Mutagenandpossiblecarcinogen

20

Nerve Gases
Nervegasorganophosphatesarethemilitarypoisonsofmostconcern

Sarin
Tokyosubwayattack
Fatalatadoseofonlyabout0.01milligramsofSarinperkilogram
ofbodymass
Singledropthroughtheskincankillahuman

21

Action of Organophosphate Poisons

Organophosphatemilitarypoisonsactonthenervoussystemby
bindingwithandinhibitingacetylcholinesteraseenzyme

22

Toxins from Biological Sources

Biotoxins
Someofthemosttoxicsubstancesknown
Botulinumtoxin
FromClostridiumbotulinumbacteriagrowingintheabsenceof
oxygen
Aslittleas1millionthofagramcanbefataltoahuman
Inprinciple,millionsofpeoplecouldbekilledbytheamountof
botulinumtoxincarriedinaterroristspocket
Bindswithnerveterminalscausingparalysisoftherespiratory
musclesanddeath

23

Ricin Biotoxin
Ricin
Verystableproteinaceousmaterialextractedfromcastorbeans
(Ricinuscommunis)
Injectionofanamountaboutthesizeofapinheadcanbefatal
Failureofkidneys,liver,andspleenalongwithmassivebloodloss
fromthedigestivetract
Hazardlessenedbyneedtoinject

24

16.6.PROTECTINGWATER,FOOD,ANDAIR
Chemicalattackonfoodsupplyatasufficientscaletocausemany
poisoningsisnotlikely
Attackonfoodsupplybymicroorganisms
Anthraxbacteriathroughairorcontact,suchasthroughmail
Shigelladysenteriaebacteriaonfoodcancauseseveredysentery
Salmonellabacteriaincontaminatedfoodcancausedebilitating
digestivetracteffects
Althoughusuallynotfatal,Salmonellaonfoodhavethepotential
tocausetemporarydisability

25

Protection of Water Supplies

Centraldistributiontolargenumbersofpeople
Susceptibletobothchemicalandbiologicalattack,thoughsuchan
attackwouldbedifficult
ArsenicinBangladeshwellwatershowspotentialofchemicalattack
Asmallamountofbotulinustoxininwatercouldkillmany
Microorganismcontaminationofdrinkingwater
Millionshavebeenkilledbywaterbornecholera,typhoid,and
dysentery
In1993,morethan400,000peopleinMilwaukeeweresickened
andover50diedfromwaterborneprotozoalCryptosporidium
parvum
InMay,2000,approximately3000peopleweremadeillandseven
diedinWalkerton,Ontario,Canada,fromdrinkingwater
contaminatedwithEscherichiacolibacteriathatproducedshiga
toxinbytransferofDNAfromShigelladysenteriaebacteria
Bacteriathatcouldbeaddeddeliberatelytodrinkingwaterinclude
Shigelladysenteriae,Vibriocholerae,andYersiniapestis.

26

Attack Through The Atmosphere

Atmosphereasamediumforchemicalattack
Meansofdelivery,suchasalowflyingcropsprayingplanewould
givewarning
Atmosphereasamediumforbiologicalattack
AnthraxsporesfromBacillusanthracisareaparticularconcern
Variolamajor,whichcausessmallpox
Francisellatularensis,whichcausestularemia
Virusesthatcauseviralhemorrhagicfevers,includingEbola,
Marburg,Lassa,andMachupo
BubonicplaguecausedbyYersiniapestisbacteriathatkilledtens
ofmillionsduringtheMiddleAges

27

16.7.DETECTINGHAZARDS
Explosives
ResiduesofTNT,RDX,andPETNexplosivesdetectedby
sophisticatedinstrumentsincludingionmobilityspectrometersand
chemiluminecencesensors
Nuclearquadrupoleresonance(NQR)maybeusefultodetect
explosivesbecauseitrespondstonitrogen,whichallmajor
explosivescontain
Canineolfactorydetection(dogsnose)

28

16.8.GREENCHEMISTRYTOCOMBATTERRORISM
Safeandsustainablegreenchemistrycanhelpcombatterrorism
Hazardoussubstancesthatmightbestolenordivertedforusein
attacksarenotmadeorusedinlargequantities
Chemicalproductsdowhattheyaresupposedtodoandareusedin
minimumquantities
Materialsandprocessesthatarelikelytoresultinviolentreactions,
fires,highpressures,andotherextremeconditionsareavoided
Potentiallyhazardousauxiliarysubstancesandflammable
materialsareavoided
Minimizesenergyconsumption,therebyreducingenergetic,high
temperatureprocessesthatmightbesusceptibletosabotage

29

Green Chemistry to Combat Terrorism

Biologicalprocessesusedingreenchemistryarecarriedoutunder
themild,lowtemperature,toxicsubstancefree,inherentlyless
hazardousconditionsconducivetobiochemicalreactions
Reducesdemandonuncertainsourcesofenergyandrawmaterials
controlledbypotentiallyhostilepopulationsthatareinherently
subjecttodisruptionandblackmail
Thepracticeofgreenchemistryrequiresexactingprocesscontrol
combinedwithrealtime,inprocessmonitoringtechniques
Conditionsthatresistsabotage
Passivesafetysystemsthatfunctionbydefaultintheeventof
failureofordeliberatedamagetointricatecontrolsystems
Example:Makingmethylisocyanateonsiteasneeded

30

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

31

Abundant, Inexpensive, Sustainable Energy is Key

32

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

33

Energy (Cont.)
Abundant,sustainableenergyrequiresthebestpracticeofgreen
chemistry,greenengineering,andindustrialecology
Increasedefficiencyofenergyutilizationisakeyaspectof
providingmoreusableenergy
Solar,wind,andbiomassenergyaresustainable,renewableenergy
sources
Fossilfuelswillplayaninterimrole,especiallyifsequestrationof
greenhousegascarbondioxidebyproductcanbeachieved
Nuclearfissionwithuraniumfuelcanprovideabundantenergy
safelywithnewgenerationnuclearreactorsandreprocessingof
nuclearfuel.

34

Energy (Cont.)
Becausewindandsolarsourcesarebynatureintermittentand
dispersedandoftenproduceelectricityinlocationsfarfromwhereit
isused,storageandtransportofenergyareveryimportant
Superconductororquantumconductorpowercablesarecandidates
fortransportofelectricalenergyfromsourcetouse
Pumpedwaterhydroelectricstorageorhighspeedflywheels
coupledwithelectricmotor/generators
Elementalhydrogen,H2,willbewidelyusedforenergystorage
andtransportaswellasforfuel,movedbypipelineandusedto
produceelectricitydirectlyinfuelcells
Hydrogenfromelectrolysisofwater
Directphotoconversionofwatertohydrogenandoxygenmay
eventuallybecomepractical

35