Detoxification of Chemical Warfare Agents : From WWI to Multifunctional Nanocomposite Approaches

150 Pages·2018·6.54 MB·English

by  Dimitrios A. Giannakoudakis

Dimitrios A. Giannakoudakis
Teresa J. Bandosz
Detoxification
of Chemical
Warfare Agents
From WWI to Multifunctional
Nanocomposite Approaches
fi
Detoxi cation of Chemical Warfare Agents
Dimitrios A. Giannakoudakis
Teresa J. Bandosz
fi
Detoxi cation of Chemical
Warfare Agents
From WWI to Multifunctional Nanocomposite
Approaches
123
Dimitrios A.Giannakoudakis Teresa J.Bandosz
TheCity College ofNew York Department ofChemistry
TheCity University ofNew York TheCity Collegeof NewYork
NewYork,NY TheCity University ofNew York
USA NewYork,NY
USA
ISBN978-3-319-70759-4 ISBN978-3-319-70760-0 (eBook)
https://doi.org/10.1007/978-3-319-70760-0
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“I fear it will produce a tremendous scandal
in the world…The higher civilization rises,
the viler man becomes”, One German
general wrote to his wife during WWI.
This work is dedicated to all the casualties of
WWI
Acknowledgements
The authors are grateful to US ARO for support of this research (Grant #
W911-13-0225, Insight into Multifunctional Reactive Adsorbents: Engaging
Chemistry, Porosity, Photoactivity and Conductivity into Decontamination
Process). The contributions of all who worked on the CWAs project in our labo-
ratory:JavierA.Arcibar-Orozco,MarcFlorent,RajivWallace,JoshuaK.Mitchell,
and Karifala Kante are highly appreciated. This research journey would be not so
beautifulandproductivewithouttheircontribution.Lastbutnotleast,weespecially
acknowledgetheinvolvementofDr.ChristopherKarwackiofEdgewoodChemical
Biological Defense Center. The fruitful conversations with him helped us to better
understand the CWA decontamination problems.
DAG would like to express his supreme gratitude the Graduate Center of the
City University of New York for the opportunity in order to obtain his Doctor of
Philosophy in chemistry degree and his third master degree. He would like also to
acknowledge the financial support through the study abroad scholarships from
Onassis Foundation and AG Leventis Foundation.
But above all, DAG issincerely and wholeheartedly thankful tohis mentor and
coauthor of this book, Prof. Teresa J. Bandosz, for the unique and totally worthy
opportunity to collaborate for three and half years during his doctoral studies and
for six months as a research assistant. The quality and quantity of the “adsorbed”
knowledge, continuous guidance, and direct or indirect support during this ulti-
mately interesting research journey will never be forgotten. This collaborative
journey ended with emotions of admiration and respect.
ix
Contents
1 Chemical Warfare Agents (CWAs). . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 The History of Chemical Warfare Agents . . . . . . . . . . . . . . . . . . 1
1.2 International Agreements Against CWAs . . . . . . . . . . . . . . . . . . . 2
1.3 Classification of Chemical Warfare Agents. . . . . . . . . . . . . . . . . . 3
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2 World War I: Militarization of Chemistry . . . . . . . . . . . . . . . . . . . . 5
2.1 The Chronicle of the Vast Scale Usage of CWAs:
The Road to Mustard Gas. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2 Casualties and Fatalities of WWI. . . . . . . . . . . . . . . . . . . . . . . . . 9
2.3 First Protection Attempts: Pads, Helmets, and Gas Masks. . . . . . . 14
2.3.1 The Germans. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.3.2 The British . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.3.3 The French . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.3.4 The Italians. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
2.3.5 The Russians. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.3.6 The Americans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3 Mustard Gas: The King of CWAs . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.1 Mustard Gas. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
3.2 Mustard Gas Deployment Post the WWI . . . . . . . . . . . . . . . . . . . 28
3.3 Proposed Decomposition Pathways of HD . . . . . . . . . . . . . . . . . . 29
3.4 The Surrogate of Mustard Gas . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.4.1 Detoxification Pathways of the Mustard Gas
Surrogate, CEES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
xi
xii Contents
4 Current Protection Against CWAs . . . . . . . . . . . . . . . . . . . . . . . . . . 33
4.1 Whetlerites: The Improved Military Activated Carbon . . . . . . . . . 33
4.2 Research on New Adsorption/Detoxification Materials . . . . . . . . . 34
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
5 New Approaches in the Detoxification of CWAs. . . . . . . . . . . . . . . . 37
5.1 Zinc (Hydr)Oxide-Based Multifunctional Nanocomposites . . . . . . 37
5.1.1 One-Pot Wet Precipitation of Zinc (Hydr)Oxide . . . . . . . . 37
5.1.2 Zn(OH) Versus ZnO: The Key Role of the Hydroxyl
2
Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5.1.3 Effect of GO Phase in Zn(OH) /GO Composites
2
on the Extent of Photocatalytic Reactive Adsorption . . . . . 57
5.1.4 AuNPs and AgNPs Embedded in Nanostructured
Composites of Zinc (Hydr)Oxide/GO . . . . . . . . . . . . . . . . 76
5.2 Zirconium (Hydr)Oxide-Based Multifunctional
Nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
5.2.1 Effect of GO Phase in ZR(OH) /GO Composites
4
on the Extent of Catalytic Reactive Adsorption . . . . . . . . . 90
5.2.2 AgNPs Embedded in Zirconium Hydroxide/GO
Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
6 Path Towards Future Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
6.1 Oxidized Graphitic Carbon Nitride Nanospheres
as a New Composite Component. . . . . . . . . . . . . . . . . . . . . . . . . 125
6.1.1 Graphitic Carbon Nitride . . . . . . . . . . . . . . . . . . . . . . . . . 125
6.1.2 Oxidized Graphitic Carbon Nitride Nanospheres . . . . . . . . 126
6.1.3 Graphitic Carbon Nitride Nanospheres as CEES
Detoxification Media . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
6.1.4 MOFGCNox Composites as Detoxification Media. . . . . . . 129
6.2 Mixed (Hydr)Oxides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
6.3 Reactive and Smart Textiles . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
6.3.1 Porous Carbon Fabrics. . . . . . . . . . . . . . . . . . . . . . . . . . . 135
6.3.2 Cotton Fabrics with Deposited Ferrihydrite . . . . . . . . . . . . 137
6.3.3 Smart Textiles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
Chapter 1
Chemical Warfare Agents (CWAs)
1.1 The History of Chemical Warfare Agents
Theextendedusageofchemicalsasweaponsdatessinceclassicaltimes,whenlighting
of bonfires, irritant smokes, and several compositions of pitch, petroleum, and sulfur
(Greekfire)deliveredaseriousadvancementforamasstroopelimination.Evenancient
historyindicatestheuseoftoxicchemicalstodefeatenemies.Homermentionedinhis
epics(theIliadandtheOdyssey)theuseofpoisonsarrowsinTrojanWar(around1200
BCE)[1].Poisonousheart-toxicextractsfromhelleboreplantswereusedbyAthenian
forces in 600 BCE to taint the water supply during the besiege of Kirrha against
Spartans [1]. Around 120 years later, Peloponnesian military used sulfur fumes to
trigger off the evacuation of the city of Plataea [2]. In the middle of the eighteenth
century(1845),theFrenchtroopscorneredmorethan1000peopleintoacaveduring
the conquest of Algeria and executed them using smoke.
TheFirstWorldWar(WWI)broughtoutaprolongedvastscaleusageofchemical
warfareagents(CWAs),whichcanbeconsideredasthesaddestrealityinthemodern
history.Morethan50differentCWAsweredeployed,whileabove3000compounds
wereinvestigatedaspotentialweapons[3].EventhoughitisbelievedthattheGerman
armywasthefirstonetousepoisongases,thatracewasinfactopenedbytheFrench
army that first deployed tear gas grenades in 1914 [4]. Since that time, the active
involvement of chemistry in the war has begun. Many compounds were afterward
tested in the battlefields as CWAs. Most CWA-related injuries and deaths during
WWIwerelinkedtothreetoxiccompounds:chlorine,phosgene,andsulfurmustard.
AtthebeginningofWWI,theGermanmilitaryestablishedresearchcenterstodevelop
chemicalsasweaponsofmassdestruction.Manyrecognizedscientistswereinvolved
inthesynthesisofCWAs.ThatlistincludesNobelPrizelaureatessuchasMaxPlanck
(Physic, 1918), Fritz Haber (Chemistry, 1918), Wulther Nernst (Chemistry, 1920),
James Franck (Physic, 1925), Gustac Hertz (Physic, 1925), and Otto Hahn
(Chemistry, 1944). The Allied forces did not stay behind, and they also started an
extensive research on the development of CWAs, as well as on protection medias,
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