EDGEWOOD CHEMICAL BIOLOGICAL CENTER U.S. ARMY RESEARCH, DEVELOPMENT AND ENGINEERING COMMAND

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1 EDGEWD CHEMICAL BILGICAL CENTER.S. ARMY RESEARCH, DEVELPMENT AND ENGINEERING CMMAND ECBC-TR-830 DECNTAMINATIN EFFICACY F CANDIDATE NANCRYSTALLINE SRBENTS WITH CMPARISN T SDS A-200 SRBENT: REACTIVITY AND CHEMICAL AGENT RESISTANT CATING PANEL TESTING Gerge W. Wagner RESEARCH AND TECHNLGY DIRECTRATE Nvember Apprved fr pbli release; distribtin is nlimited. ABERDEEN PRVING GRND. MD

2 Dislaimer The findings in this reprt are nt t be nstred as an ffiial Department f the Army psitin nless s designated by ther athrizing dments.

3 REPRT DCMENTATIN PAGE Frm Apprved MB N Pbli reprting brden fr this lletin f infrmatin is estimated t average 1 hr per respnse, inlding the time fr reviewing instrtins, searhing existing data sres, gathering and maintaining the data needed, and mpleting and reviewing this lletin f infrmatin Send mments regarding this brden estimate r any ther aspet f this lletin f infrmatin, inlding sggestins fr reding this brden t Department f Defense, Washingtn Headqarters Servies, Diretrate fr Infrmatin peratins and Reprts ( ), 1215 Jeffersn Davis Highway. Site 1204, Ariingtn, VA Respndents shld be aware that ntwithstanding any ther prvisin f law, n persn shall be sbjet t any penalty fr failing t mply with a lletin f infrmatin if il des nt display a rrently valid MB ntrl nmber PLEASE D NT RETRN YR FRM T THE ABVE ADDRESS 1. REPRT DATE (DD-MM-YYYY) 3. DATES CVERED (Frm - T) 2. REPRT TYPE Final XX-ll TITLE AND SBTITLE Dentaminatin Effiay f Candidate Nanrystalline Srbents with Cmparisn t SDS A-200 Srbent: Reativity and Chemial Agent Resistant Cating Panel Testing May t a. CNTRACT NMBER W9HSR-07-C b. GRANT NMBER 5. PRGRAM ELEMENT NMBER 6. ATHR(S) Wagner, Gerge W. 5d. PRJECT NMBER 0714C 5e. TASK NMBER 5f. WRK NIT NMBER 7. PERFRMING RGANIZATIN NAME(S) AND ADDRESS(ES) DIR. ECBC. ATTN: RDCB-DRP-F, APG, MD PERFRMING RGANIZATIN REPRT NMBER ECBC-TR SPNSRING / MNITRING AGENCY NAME(S) AND ADDRESS(ES) 10. SPNSR/MNITRS ACRNYM(S) 11. SPNSR/MNITRS REPRT NMBER(S) 12. DISTRIBTIN / AVAILABILITY STATEMENT Apprved fr pbli release; distribtin is nlimited. 13. SPPLEMENTARY NTES Limited data frm ECBC-TR-277 and ECBC-TR-302 are referened herein per permissin f NanSale Crp. (Manhattan. KS) and the athrs. 14. ABSTRACT-LIMIT 200 WRDS Several nanrystalline reative srbents, f varied partile size and srfae area, were examined as dentaminating srbents. The reatin kinetis f VX. GD, and HD were determined in additin t effiay fr srfae dentaminatin f Chemial Agent Resistant Cating (CARC) paint. The Srbent Den System (SDS) A-200 srbent was tilized as a ntrl. The best srbent fr VX was nti0 2, whih enabled a half-life f <2 min. Cmparable half-lives fr GD (tens-fmintes) were bserved n nti0 2, nmg, and the mmerial FAST-ACT" srbent. Half-lives f a few t many hrs were bserved fr HD n nal : t, nti:, FAST-ACT*, and A-200. bt nly with sffiient srfae hydratin. Regarding reativity nly, A-200 did nt perfrm as well as the nanrystalline srbents, espeially fr VX and GD. Hwever, all f the srbents. A-200 inlded, prvided fr the mparable remval f HD and GD frm CARC panels, a. 75 and 87%, respetively. An apparent srfae-prsity f 0.8 /m" fr the CARC paint is presmed respnsible fr this lw effiay. Smaller srbent partile sizes (<5 M) did nt inrease srfae dentaminatin effiay. 15. SBJECT TERMS Dentaminatin Nanrystalline 16. SECRITY CLASSIFICATIN F: a. REPRT b. ABSTRACT A-200 CARC. THIS PAGE VX GD 17. LIMITATIN F ABSTRACT L Reative srbents Srfae dentaminatin 18. NMBER F PAGES 62 HD 19a. NAME F RESPNSIBLE PERSN Sandra J.Jhnsn 19b. TELEPHNE NMBER,,nlde area de) (410) Standard Frm 298 (Rev. 8-98) Presribed by ANSI Std. Z39 18

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5 EXECTIVE SMMARY In a perative researh and develpment agreement, the.s. Army Edgewd Chemial Bilgial Center tested several f NanSale Crpratin's (Manhattan, KS) nanrystalline reative srbents, f varied partile size and srfae area, fr dentaminatin effiay f hemial agents. The rrently-fielded Srbent Den System (SDS) A-200 srbent was tilized as a ntrl. Reatin kinetis with neat VX, GD, and HD were determined in additin t effiay fr the srfae dentaminatin f Chemial Agent Resistant Cating (CARC) painted panels. Fr VX, the best srbent was nti:, whih enabled a half-life fr srbed VX f less than 2 min. Cmparable half-lives fr GD (tens f mintes) were bserved n nti:, nmg, and the mmerial FAST-ACT" (NanSale) srbent. Half-lives f a few t many hrs were bserved fr HD n nafi, nti:, FAST-ACT", and A-200, bt nly with sffiient srfae hydratin. With regard t reativity nly, A-200 did nt perfrm as well as the nanrystalline srbents, espeially fr VX and GD. Hwever, all f the srbents, A-200 inlded, prvided fr the mparable remval f HD and GD frm CARC panels, a. 75 and 87%, respetively. An apparent srfae-prsity f 0.8 /m" fr the CARC paint is presmed respnsible fr this lw effiay. Smaller srbent partile sizes (>5 //m) did nt inrease srfae dentaminatin effiay fr CARC paint, bt did exhibit enhaned GD reativity (even thgh they pssessed lwer srfae area). High srfae area favred VX reativity. Reativity fr HD was nt signifiantly enhaned by either small partile size r high srfae area srbent versins.

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7 PREFACE The wrk desribed in this reprt was athrized nder perative researh and develpment agreement Prjet N. 0714C and Cntrat N. W911SR-07-C The wrk was started in May 2008 and mpleted in tber The se f either trade r manfatrers' names in this reprt des nt nstitte an ffiial endrsement f any mmerial prdts. This reprt may nt be ited fr prpses f advertisement. This reprt has been apprved fr pbli release. Registered sers shld reqest additinal pies frm the Defense Tehnial Infrmatin Center; nregistered sers shld diret sh reqests t the Natinal Tehnial Infrmatin Servie. Aknwledgments The athr thanks Nile K. Flether and Tara L. Sewell fr assistane with the hemial agent peratins. Helpfl disssins regarding Chemial Agent Resistant Cating panel testing with Lawrene R. Prell and Philip W. Bartram are grateflly aknwledged.

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9 CNTENTS 1. INTRDCTIN 9 2. EXPERIMENTAL PRCEDRES Materials Air-Expsre Reativity Testing Panel Testing RESLTS AND DISCSSIN Reativity Testing nmgsrbents nti: nal, and A FAST-ACT and FAST-ACT Reativity Testing Smmary Panel Testing CNCLSINS 21 LITERATRE CITED 23 APPENDIXES A - REACTIVITY TEST RAW KINETIC DATA 25 B - REACTIVITY TEST SELECT MAS NMR SPECTRA 33 C - PANEL TEST DATA 61

10 FIGRE Illstratins f Cntat and Hazard Tests t Determine Residal Agent Present n CARC Panels 19 TABLES 1. Reslts f Bartram and Lynn fr the Dentaminatin f VX, GD, and HD n npainted Alminm Panels 9 2. Reslts f Bartram and Lynn fr the Reatins f VX, GD, and HD n FAST-ACT and A Reslts f Davis et al. fr the Dentaminatin f VX, TGD, and HD n CARC-Painted Steel Panels by A-200 at 25 C Partile Size and Srfae Area f Stdied Samples Half-Lives fr VX, GD, and HD Added t Candidate Srbents Shrtest, Sstained Half-Lives Exhibited by Srbents, Fresh r Air- Expsed, fr VX, GD, and HD Srbent Reativity Ranking Based n bserved Agent Half-Lives Panel Test Reslts fr Srbent Dentaminatin f CARC Paint 20

11 DECNTAMINATIN EFFICACY F CANDIDATE NANCRYSTALLINE SRBENTS WITH CMPARISN T SDS A-200 SRBENT: REACTIVITY AND CHEMICAL AGENT RESISTANT CATING PANEL TESTING 1. INTRDCTIN The hemial warfare agents, VX, GD, and HD, have been well-knwn t srb and reat n metal xides sh as almina fr mre than a deade. 1 Indeed, almina is the ative ingredient (A-200)" ntained in the Srbent Dentaminatin System (SDS). ' Yet, mpared t nventinal metal xides, nansize metal xides may affrd enhaned reativity wing t their larger srfae areas, nsal expsed lattie planes, and greater prprtins f highlyreative edge and rner "defet" sites." ( Ths, reatins f nansize Mg, Ca, and almina with VX, GD, and HD were ndertaken. 7 ' 89 in. 11 Bartram and Lynn'" ' assessed the effiay f a mmerial, nanrystalline Mg reative srbent, FAST-ACT K, and mpared it t A-200. In the Phase I stdy, 10 the effiay fnd fr the dentaminatin f VX, GD, and HD n (npainted) alminm panels, is shwn in Table 1. Fr the mst part, exept fr GD at the highest 12.5 srbent-t-agent rati, Bartram and Lynn nted n signifiant differene between the tw srbents with regard t srfae den fr the agents n npainted alminm (lwer ratis stdied shwed nnsignifiant differene fr GD). 10 Table 1. Reslts f Bartram and Lynn fr the Dentaminatin f VX, GD, and HD n npainted Alminm Panels' Srbent Agent Srbent Applied (mg) Srbent:Agent Rati % Den VX FAST-ACT GD HD VX A-200 GD HD in. diameter panels sed. Cntaminatin level 10 g/m". 15 min agent dwell time. Three repliate panels. Per FM3-5. NBC Dentaminatin, DA, Washingtn, DC, Jly 2000, immediate dentaminatin is expeted t mmene within 15 min fllwing depsitin f agent. Reatin rate fr VX n FAST-ACT was 17 and 15 h vs. 31 and 17 h, and CD's reatin rate n FAST-ACT was 1.3 and 2.1 h vs. 4.1 and 21 h.

12 In Phase II, Bartram and Lynn fllwed the reatin kinetis f VX, GD, and HD srbed n FAST-ACT and A-200 by MAS NMR. They fnd that rbbing the agent int the srbent signifiantly inreased the dempsitin f VX and GD, bt nt that f HD, and that the reatin rates f the agents were nt signifiantly different n the tw srbents. These reslts are smmarized in Table 2. Table 2. Reslts f Bartram and Lynn" fr the Reatins f VX, GD, and HD n FAST-ACT and A-200 VXt 12 GDt /2 HDt /2 Srbent Initial (min) Final Initial (min) Final (h) Initial Final (h) FAST- Nrmal h h 31 ACT h min 25 Rbbed" min <5 C h 26 < 5 C - <4 C h 12 A-200 Nrmal h h h l.h 16 Rbbed" <5 C - <4 C - 45 min 19 <4 C - -4' - 19 min 20 a 4-6 L age nt added t \' mg FAST-ACT r 2-3 L added t a. 100 mg A-200 witht rbbing r agitatin. b mg FAST-ACT rbbed nt 6 L agent r mg A-200 rbbed nt 4-6L agent ntained n npainled almina panels. e Agent nt deteted, pper-limit t, :2 estimated frm first time pint. Davis et al. 4 perfrmed A-200 dentaminatin effiay testing fr VX, TGD, and HD n a variety f srfaes, inlding Chemial Agent Resistant Cating (CARC) paint; data fr the latter srfae are shwn in Table 3. Table 3. Reslts f Davis et al. fr the Dentaminatin f VX, TGD, and HD n CARC-Painted Steel Panels by A-200 at 25 C* Agent CARC Bare Stainless Steel Revery Effiieny frm Stainless Steel (%) (%) (%) VX TGD HD m diameter panels ntaminated with 10 g/nr agent. N agent dwell time. 5 min srbent dentaminatin time. Three repliate panels. 10

13 These reslts reqire frther mment bease f the mpliated natre f the CARC srfae, whih is knwn t be penetrated and sftened by the agents. " Ths, wing t srptin f agent int CARC, time is f the essene fr its dentaminatin. The lnger ne waits, the smaller is the amnt f agent remaining n r near the srfae that an be easily remved, espeially by a nn-penetrating dentaminant sh as a slid srbent. The rder f penetrating/sftening ability f the agents is HD» VX > GD; 12 therefre, HD tends t be the mst diffilt t remve r den n CARC, fllwed by VX; GD is by far the easiest. Hwever, the sitatin hanges fr thikened GD (TGD) wing t the need t adeqately disslve r therwise remve the stiky sbstane frm the srfae. This is espeially prblemati fr CARC de t its dll, matte-finish. Ths, the srfae rghness wld tend t ling and grab nt thikened agents mre s than a smth metal r glass srfae. These effets are ertainly evident in the reslts in Table 3 where, nsidering the simple liqid agents, less HD (94.9%) is able t be remved frm the CARC srfae than VX (97.6%). The lw remval f TGD (72.6%) is ndbtedly de t its zing int the rghsrfae f CARC and the inability f the A-200 srbent t qikly srb this viss, thikened agent. Indeed, n bare (smth) stainless steel, TGD remval jmps t 99.1 %. It is imprtant t frther nte that the remval effiieny f VX, and espeially that f HD, wld be nsiderably less had a nn-zer (i.e., 15 min) dwell time been emplyed. The reslts fr TGD wld prbably nt be s affeted by a finite dwell time as the presene f the thikener tends t slw the srptin f agent int a sseptible srfae. 1 " Finally, the lw reveries f VX and HD frm the stainless steel srfae (51.7 and 71.0%, respetively) is prbably de t agent rnningff the edge f the pn (as previsly nted by Bartram and Lynn). ' This tends t nt be a prblem fr TGD, whih flws very slwly; ths, the revery f 100%. It is the aim f the present stdy t examine several nanrystalline materials t determine if they are sperir t FAST-ACT and t mpare them t the perfrmane f A-200. Basially, a dentaminatin srbent an exel in ne r tw ways: 1) qikly reat with/destry srbed agent (kinetis) and 2) remve/srb agent frm srfaes t lwest pssible levels. Sme f the individal srbents have been varied in terms f partile size and srfae area t determine what impat, if any, these attribtes have n reatin kinetis and remval effiieny. T give the andidate srbents a hane t demnstrate lear speririty, prpsely-hallenging tests were ndertaken. The first test, perfrmed by MAS NMR, assesses the ability f a srbent t reat with a single, 5 L drp f agent witht rbbing r any external agitatin. The ratinale fr this is that sh rbbing r agitatin wld indeed imprve any innate reativity (as demnstrated by Bartram and Lynn)" bt that a srbent that an fntin witht rbbing r mixing is learly sperir t ne that annt. The send test assesses the ability f a srbent t dentaminate CARC paint sing the 15 min dwell time mentined abve fr the immediate dentaminatin senari. Ths, a srbent whse partiles are mst adept at slipping int mir-raks and revies f nn-smth srfaes t ferret t and srb mirpls f agent will exhibit the best effiay. Finally, the ability f a srbent t remain effiais in air (air-stability) was assessed by repeating the reativity test fllwing 24 h expsre f the srbent t air. 11

14 2. EXPERIMENTAL PRCEDRES 2.1 Materials Srbent samples were reeived frm NanSale Crpratin (Manhattan, KS) in sealed plasti jars ntaining ~1 g. The srbents were either sed as-reeived r sbjeted t 24 h air-expsre (see belw). Fr the as-reeived material, air-expsre was limited by pening a fresh jar jst prir t eah experiment. Initially, the fllwing five srbents were examined: 1. NanAtive Magnesim xide Pls, lt # (nmg #1) 2. NanAtive Magnesim xide, lt # (nmg #2) 3. NanAtive Titanim xide, lt # (nti : #1) 4. NanAtive Alminm xide Pls, lt # (nal ) 5. Gild Almina (A-200) The fllwing fr srbents were then additinally examined: 1. NanAtive Ti0 2 2, lt # (nti0 2 #2) 2. Mdified Magnesim xide Pls, lt # B1 (nmg #3) 3. FAST-ACT, lt # FAST-ACT 2, lt # The prperties f the abve materials are listed in Table 4. 12

15 Table 4. Partile Size and Srfae Area f Stdied Samples Partile Size Distribtin (Vlme %) Srfae Area Sample <5m 5-20m >50m m2/e nmg#l nmg# ntj0 2 # n\l 2 0, nlk), # Mg # FAST-ACT FAST-ACT A Air-Expsre T assess the sensitivity f the srbents t air, a. 0.5 g samples f eah srbnt was spread nt a piee f weighing paper and allwed t stand fr 24 h in air. The weight gain was measred and the expsed sample was sbjeted t a send agent reativity test t mpare its perfrmane with the fresh, as-reeived material. 2.3 Reativity Testing Reativity testing was dne by MAS NMR sing Varian INVA 400 r nitypls 300 NMR spetrmeters eqipped with Dty Sientifi 7 mm MAS prbes. In a typial experiment, a 10 L syringe was sed t injet 5 L neat liqid agent int the middle f a lmn f srbent ntained in a 7 mm MAS NMR rtr (Dty Sientifi). The rtr was sealed with dble -ring endaps and spetra were taken peridially t mnitr the reatin prgress and identify prdts. l3 C-labeled HD (HD*) was emplyed t enhane sensitivity as these reatins were mnitred by C MAS NMR. P MAS NMR was emplyed t mnitr the 13/ reatins f VX and GD. Spetra were referened t TMS (0 ppm, C) and 85% ftpc»4 >ii (ppm, 'P) 2.4 Panel Testing Tw inh diameter CARC-painted alminm pns were emplyed (area = 20 m"). Six repliate panels were emplyed fr eah test. Twenty milligrams f agent (10 g/m") was depsited nt eah panel by applying 16 L HD (d = 1.27 g/nr) r 20 L VX r GD (bth d = 1.0 g/nr) in a. 2 L drps. The drps were then manally spread arss eah panel sing a piee f parafilm t ensre nifrm srfae verage. The panels were vered with an inverted Petri dish (t prevent nde evapratin f agent) and allwed t stand fr 15 min. At the end f the 15 min agent dwell perid, 200 mg f pre-weighed, andidate srbent was emptied frm a 4 ml srew ap vial nt eah panel and evenly-distribted arss 13

16 the panel with a mirspatla. Then a 1 kg 2 in. diameter weight vered with alminm fil n the bttm was sed in the manner f Bartram and Lynn 10 t rb the srbent n eah panel: five lkwise trns fllwed by five nterlkwise trns. This press tk 1 min r less. Sme exess srbent was ejeted ver the side f the panel dring the rbbing press. The remaining exess srbent was immediately sraped ff with a mir spatla; hwever, a fine ating f pwder still invariably lng t the rgh CARC srfae. N additinal atin was taken t remve this fine ating, whih wld als ertainly remain n treated CARC srfaes in the field. T assess the amnt f agent remaining, a ntat test was first emplyed: eah panel was plaed n a 30 C slide warmer (t simlate being thed by a warm, bare hand) and a 2 in. latex (Dental Dam) disk was plaed n tp f eah panel, fllwed by a 2 in. alminm fil ver (t prevent agent frm migrating past the latex). A 1 kg weight was plaed n tp f the alminm fil ver t exert pressre dring a ntat perid f 15 min. At the end f the 15 min ntat perid, the latex and fil disks were remved frm eah panel and extrated in 20 ml hlrfrm fr 1 h. The panel itself was then extrated in a vered weighing dish with 10 ml hlrfrm, als fr 1 h, t determine the residal agent hazard. The extrats were analyzed by 'H and/r 3I P NMR t determine the amnt f agent present. 3. RESLTS AND DISCSSIN 3.1 Reativity Testing bserved half-lives fr 5 L VX, GD, and HD added t the fresh, as-reeived srbents and the 24 h air-expsed materials are given in Table 5 (raw kineti data and selet MAS NMR spetra Appendies A and B). wing t previsly nted diffsin effets, 7 sme reatins exhibited an initial fast reatin fllwed by a mh slwer, diffsin-limited reatin; ths, in these instanes, separate half-lives are reprted fr the tw regimes nmg Srbents Fr the nmg srbents, GD tended t reat qikest with half-lives n the rder f tens f mintes. That the GD reatins did nt exhibit severe diffsin limitatins an be asribed t bth its rather high vlatility (mpared t VX and HD) and gd water slbility (GD is slble in water, bt nt misible), the latter attribte presmably allwing it t disslve and diffse within srfae-bnd water layers. Nte, hwever, that despite air-expsre and the attendant ptential water adsrptin, sme degradatin f the GD reativity rred. This is easily nderstd by the bservatin that the nmg srbents tended t gain the mst weight pn air-expsre (pwards f 30%) and that l3 C MAS NMR (spetra B5-6 in Appendix B) shwed the frmatin f arbnate (C3 ) n this material as a reslt f reatin with ambient C2 in the air. Sh a press wld tend t netralize the very basi Mg srfae; ths, the deleteris effet n GD hydrlysis. Nte that arbnate was nt deteted n any f the fresh nmg (spetra B5-7 in Appendix B), whih is nsistent with gd qality ntrl dring their manfatre and pakaging t avid nde air-expsre. 14

17 VX als tended t reat mre qikly with fresh nmg (half-life n the rder f hrs) and did nt appear t be severely diffsin-limited n nmg #1, perhaps as a reslt f spntanes wetting f this partilar nmg. Hwever, air-expsre did ase a majr lss in bserved VX reativity/diffsin. In its prtnated state, VX is water slble. Hwever, with a pk a f 8.6, 13 VX is mst likely "free-based" by the basi Mg srfae int the nprtnated state; ths, it wld sffer limited water slbility and, hene, diffsin (barring spntanes wetting), within srfae water layers. Fr HD n nmg, the reatin appears entirely diffsin-limited (in n small pail de t its water inslbility) - there is n fast, initial reatin. Yet, nsistent with the very basi nmg srfae, the majr reatin mehanism fr HD is eliminatin t its vinyl and divinyl prdts, varying frm 50% n nmg #1 t 67% n nmg #2 and >90% n nmg #3 (the latter material evidently pssesses the highest basiity). f rse, as a reslt f the afrementined arbnatin/netralizatin f srfae basiity, eliminatin is rtailed in the air-expsed samples t <10% in nmg #1 and 50% in nmg #2, and the verall reativity sffers. It is frther interesting t nte that air-expsre reslted in greater arbnatin f nmg #2 mpared t nmg #1 (as indiated by their C MAS NMR spetra, B6 and B5, respetively. Appendix B) whih is nsistent with the frmer's higher apparent basiity. Presmably, the highest basiity nmg #3 wld have sffered the mst arbnatin, bt it was nt tested. Regarding the varied partile size and srfae area f the nmg srbents stdied, GD tended t reat qikest with the fresh srbent pssessing the smaller partile size distribtin and lwer srfae area, nmg #2. Hwever, pn air-expsre, nmg #1 was able t retain its reativity better. That this is s is perhaps related t its larger partile size, whih wld tend t reat slwer with ambient C:. This is nsistent with the smewhat lwer weight gain f the nmg #2 srbent dring 24 h air-expsre, wt % vs wt% fr nmg #1. HD tended t reat eqally well with the tw fresh materials, bt, again, the largerpartile material tended t retain its reativity better dring 24 h air-expsre. As fr VX, it tended t reat better with the larger-partile size, higher-srfae area nmg #1, even after 24 h air-expsre. 15

18 Table 5. Half-Lives fr VX, GD, and HD Added t Candidate Srbents Srbent Treatment VX GD HD(h) nmg #1 fresh 4.2 h 24 min 15 air-expsed 9.3/43 h 28 min 24 nmg #2 fresh 1.3/11 h 15 min 15 air-expsed 53 h 47 min 35 nmg #3 fresh nt dne nt dne 2.3/24 air-expsed nt dne nt dne nt dne nti0 2 #l fresh 23 min (rn 1) 2.8 h 5.4/17 23 min (rn 2) air-expsed <2 min (rn 1) 29 min 1.5/11 <2 min (rn 2) nti0 2 #2 fresh 36 min 17min/1.3h 1.5/31 air-expsed 8.5 min 9.3 min/23 min 1.5/10 nal fresh 2.1/32 h 3.0 h 6.3/34 air-expsed 2.8/31 h 2.0 h 5.7 FAST-ACT fresh 41 min/2.2h 16 min 4.0/38 air-expsed 26 min/3.9 h 34 min 4.3/14 FAST-ACT2 fresh 55 min 3.3 h 1.2 h 3.4/28 air-expsed 1.5 h 24 min 2.2/13 A-200 fresh 7.4/56 h h 29 air-expsed 14/54 h 4.0 h nti Althgh VX may be nprtnated and, ths, pssess limited water slbility within srfae water layers n nmg, this is bvisly nt the ase fr nti0 2 where the half-life fr VX is an astndingly shrt 23 min. Mrever, pn air-expsre, nti0 2 piks p 13-16% water, frther enhaning VX diffsin and reatin sh that the half life is nbelievably nder 2 min! Sh fast VX reatins, where an apparently nn-diffsin limited half-life f <30 min rs, has previsly been seen n nantblar titania (NTT). 1 It is knwn that the srfae hydrxyls 15 f titania (and NTT 16 ) are mre aidi than Mg, and even Al 2 0*3 (basi engh t eliminate HD), ths anting fr the presmed VX prtnatin and failitated diffsin (espeially when sffiient hydratin layers are present) n nti0 2 (and NTT). That the VX halflives are a bit lnger n nti0 2 #2 ld be de t frtits differenes in water ntent; fr example, pn air-expsre, it piked p nly 15.6% weight mpared t 20.8% fr nti0 2 #1. The effet f sffiient hydratin layers n (water-slble) agent diffsin is als apparent in the signifiantly shrter half-life f GD (29 min) n air-expsed nti0 2 #1 mpared t the fresh material (2.8 h). Fr nti0 2 #2, the behavir f GD is qite different in that, fllwing an initially fast reatin, a diffsin-ntrlled reatin enses (albeit still at a faster rate than n nti0 2 #1). It is nt lear if these differenes are de t partile mrphlgy, srfae harateristis, r hydratin effets. Hwever, the HD reslts sggest that nti0 2 #1 has the highest initial water ntent as its hydrlysis is fastest n this as reeived material. Bt after airexpsre bth nti0 2 frmlatins pssess virtally indistingishable HD-reatin behavir. 16

19 Like nmg, GD tended t reat best with the smaller-partile nti: #2, befre and after 24 h air-expsre. Als like nmg, VX nversely reated best with the larger-partile ntii #1, befre and after 24 h air-expsre. Bth materials pssessed idential srfae areas. Again, HD did nt appear t favr ne material better than the ther nal and A-200 Fr HD n nahch, the air-expsed sample nly piks p 1-6% water bt this is evidently engh t rede the (diffsin-limited) half-life frm 34 t 5.7 hthe shrtest sstained half-life fr HD bserved n any f the srbents. Besides hydrlysis, similar bt minr amnts f HD eliminatin prdts are bserved n bth fresh and air-expsed material (srfae arbnatin f the mst basi sites des nt seem t r as it des with nmg). The GD half-life is similarly reded frm 3 t 2 h (yet still slwer than n the mre basi nmg srfae). Bt fr VX there is virtally n hange; it is extremely persistent n bth dry and hydrated materials. The reasn fr the persisteny f VX n almina, and Mg, fr that matter, an be attribted t the tight binding f its hydrlysis prdt EMPA t these basi srfaes (as deteted by,! P MAS NMR); 7 ' 9 ths, EMPA is nable t assme its sal rle t atatalytially hydrlyze VX. 1 "' EMPA des nt bind tightly t the nti: (nr t the NTT 14 ) srfae, s it remains free t dismantle VX with aplmb. These bservatins fr nak.i als apply t A-200 whih tends t pik p even less water pn air-expsre (1-2%). In a similar manner, VX als remains persistent n bth the fresh and air-expsed materials as EMPA is still sidelined. Hwever, the half-life fr GD is nsiderably reded n the air-expsed sample frm 13 (diffsin-limited) t 4 h as a reslt f simply piking p 1.8% water. Mdest gain is als seen fr HD reativity n the slightly wetter material, reding its half-life frm 29 t 19 h. As with nal.i, qite similar bt minr amnts f eliminatin prdts are bserved n bth fresh and wet materials FAST-ACT and FAST-ACT 2 VX reats rather well with bth FAST-ACT and FAST-ACT 2, even after airexpsre, as half-lives d nt exeed a few hrs. GD gives mixed reslts, having the shrtest half-life n fresh FAST-ACT (16 min), whih effetively dbles n the air-expsed material (34 min) whereas n FAST-ACT 2 the half-life is shrter n the air-expsed (24 min) and qite lng n the fresh (1.2 h) material. HD shws its typially slw, water-starved reativity n the dry, fresh srbents (nlike nmg, nly minr eliminatin f HD rs) whereas enhanement rs fr the air-expsed, hydrated materials. Typial weight gains are 18-24% and 22-30% fr air-expsed FAST-ACT and FAST-ACT 2, respetively. Like nmg, GD reated best with the fresh, smaller-partile size, lwer-srfae area FAST-ACT, whereas the larger-partile, higher-srfae area FAST-ACT2 maintained its reativity (atally imprving). Als like nmg. HD reated similarly with bth partile sizes. Hwever, nlike nmg, VX tended t reat better with the smaller-partile size, smaller-srfae area FAST-ACT. 17

20 3.1.5 Reativity Testing Smmary Frm the reativity reslts it is easy t see that nti*2 has the mst ptential t affrd qik, simltanes reativity fr all three agents, prvided sffiient water is present. Althgh rrent water levels f 16-21% are effetive at reding the VX and GD half-lives t <2 and 29 min, respetively, the HD half-life is still 11 h, nearly twie as lng as that f airexpsed QAI23 (5.7 h). Hwever, perhaps even higher water levels ld ahieve frther redtin in the HD half-life while maintaining, r even frther enhaning, its npreedented VX and GD reativity. With regard t partile size and/r srfae area, the smaller partile size versins f nmg, nti"2, and FAST-ACT tended t reat fastest with GD, even thse with reded srfae areas. Cnversely, VX reated best with higher-srfae area nmg, FAST-ACT, and larger-partile size nticn. Hwever, fr HD, n prnned partile size and/r srfae area effets ld be diserned. verall, nan-based srbents were highly sperir t A-200, having mh shrter half-lives, with nti: being the mst effetive. The shrtest, sstained half-lives bserved fr the agents n the srbents, either prvided by fresh r air-expsed materials, are lleted in Table 6. Table 6. Shrtest, Sstained Half-Lives Exhibited by Srbents, Fresh r Air-Expsed, fr VX, GD, and HD Agent nmg nti, nal (h) FAST-ACT A-200 (h) VX 4.2 h a <2 min b 31.0 C 1.5 h d 54.0 C GD 15 min e 23 min' 2.0 C 16 min g 4.0 C HD 15h ae llh b 5.7 C 13 h d 19.0 C '' Fresh nmg # Air-Expsed nti: #1. Air-Expsed material. d Air-Expsed FAST-ACT2. e Fresh nmg #2. f Air-Expsed nti: #2. 8 Fresh FAST-ACT. Frm the shrtest, sstained half-lives given in Table 6, rankings f the srbents with regard t their ability t reat with VX, GD, and HD in the mst expeditis manner an be gleaned. These rankings are shwn in Table 7 where half-lives f the same rder-f-magnitde are nsidered eqivalent (mintes > tens f mintes > hrs > tens f hrs). Nte that, at present, these rankings shld be nsidered tentative as a mprehensive stdy f the effet f water-ntent n the reatin kinetis, whih dramatially impats the bserved half-lives (see abve), has nt been dne. Nevertheless, this ranking sggests nti: as the srbent pssessing the mst ptential t prvide simltanes, fast reatin with all three agents, bease its effiay is by far the best fr VX; mparable t nmg and FAST-ACT fr GD; and reasnably lse t that f nal^ fr HD. Mrever, nlike nmg, nti: is nt deativated by air (see abve), rendering it a mre rbst hie fr se as a reative srbent. IN

21 Table 7. Srbent Reativity Ranking Based n bserved Agent Half-Lives vx nti0 2» FAST-ACT = nmg > nal > A-200 GD nmg = FAST-ACT ~ nti0 2 > nal > A-200 HD nal > nti0 2 ~ nmg ~ FAST-ACT «A Panel Testing Reslts fr the dentaminatin f HD and GD n CARC panels are given in Table 8. Average vales and standard deviatins are shwn fr the six-panel repliates. Cmplete data sets are given in Appendix C. Illstratin f the ntat and residal hazard (extrat) tests are shwn in the fllwing Figre. Step 1, Cntat Test with Latex Disk Latex Disk Srptin f Srfae Liqid int Latex \ X Liqid Agent ^ f f f ' ' J M f ff M t M MJ M ^ CARC Paint- Srfae Prsity 0.8 /nr Step 2, Latex Disk Remved Fllwing Cntat. Sb-Srfae Agent Remains in Grves Crevies Pres Step 3, Panel Extrated in CHCI3 Dring Extratin, Sb-Srfae Agent is Disslved Displaed frm Grves/Crevies; Pres ~LrrT^rL^i^TrtTTinjTJrj~LtrTr Figre. Illstratins f Cntat and Hazard Tests t Determine Residal Agent Present n CARC Panels. Fr blank rns (n srbent den), the amnt f HD and GD remaining fllwing the ntat test was idential (1.6 L) indiating a srfae prsity f abt 0.8 /m" fr the CARC panels as depited. As mentined in the Intrdtin, the 15 min agent dwell time has rendered HD ntieably mre diffilt t dentaminate n the CARC panels, s that nly 69 t 77% an be remved mpared t 86-87% fr the mh less penetrating/sftening GD. Frm the

22 HD % Den reslts it appears that the nmg #1 srbent (69%) may perhaps be slightly less effetive than nmg #2 (74%), nti0 2 (75%), and nal (76%), all f whih, nsidering the standard deviatin, prvide virtally idential reslts t that f the A-200 (77%). Table 8. Panel Test Reslts fr Srbent Dentaminatin f CARC Paint a H D C.I) Srbent Cntat Residal Ttal % Den Cntat Residal Ttal % Den nmg #1 1.8 (0.45) 2.4 (0.14) 4.2 (0.59) 74 (3.8) 1.7 (0.52) 0.95 (0.23) 2.6 (0.36) 87 (1.6) nmg #2 2.5 (0.21) 2.4 (0.23) 4.9 (0.40) 69 (3.8) 1.4 (0.46) 1.2 (0.17) 2.8 (0.39) 86 (2.0) nti0 2 #1 2.0 (0.56) 1.9" (0.35) 4.0 h (0.70) 75 b (4.4) 1.4 (0.098) 1.2 (0.27) 2.6 (0.23) 87 (1.2) nal (0.30) 1.4 (0.16) 3.9 (0.41) 76 (2.4) 1.2 (0.26) 1.4 (0.16) 2.6 (0.15) 87 (0.75) A (0.44) 1.3 (0.46) 3.8 (0.47) 77 (2.9) 2.0 (0.24) 0.65 (0.093) 2.6 (0.24) 87 (1.0) N Den Cntrl 0 14 (1.5) 1.6 (0.36) 16 (1.2) 98 (9.3) 12 (1.0) 1.6 (0.50) 13 (1.2) 66 (5.8) 2 in. diameter pane s ntaminated with 10 g/m" agent. 16 g HD r 20 g GD manally spread evenly arss panel. 15 min agent dwell time. 5 min srbent dentaminatin time. nits in mirgrams ([g] agent revered). % Den is the ttal perent agent remved frm panel. Six repliate panels. Standard deviatin shwn in parentheses. Average f three repliates. N srbent applied (t determine agent revery effiieny). Regarding partile size and the ptential ability f smaller partiles t ventre int the presmed small revies and lefts f the rgh CARC srfae, nal 2 03 pssesses the highest fratin f the smallest, <5 rn partiles (90.34%), yet was statistially n better at remving imbedded HD r GD than A-200, whih pssesses the lwest fratin f these small partiles (4.07%). The nly hint f a partile-size effet fr agent remval is given by the marginallybetter perfrmane f nmg #2 mpared t nmg #1, whse fratins f <5 pm partiles are and 7.65%, respetively; hwever, their % Den, 69 and 74%, are still within experimental errr (±3.8%). Ths, either the srfae featres f CARC within whih agent abides have penings signifiantly-smaller than 5 pm, r the srbent partiles able t reah the sereted agent renders insignifiant reatin/dentaminatin n the reqired time-sale (15 min). Hwever, whatever the reasn, small partiles (<5 pm) f the rrent materials d nt appear t enhane the srfae dentaminatin effiay f CARC paint. It is imprtant t nte that fr the ntrl experiment, the exellent revery f HD frm the CARC panels (98%, in the absene f applied srbent) shws that the 1 h CHC extratin predre is sffiient t rever the CARC-srbed HD. Fr the GD ntrl experiment, ntieable lss rred as sme f the GD ran ver the sides f the panel dring the 20

23 15 min dwell time; ths, explaining the lw GD revery f nly 66%. It is frther interesting t nte that the extrats f bth the GD and HD ntrls are idential, 1.6 L. Ths, the same amnt f liqid remained entrained and inaessible t be srbed by the latex disk dring the 15 min ntat hazard assessment perid (see Figre). This bservatin sggests that the CARC paint pssesses a large prsity f abt 0.8 /m 2 as depited in the Figre. Fr GD, all the srbents perfrmed identially. Ths, the panel testing prvided little insight int the tre ptential f the andidate srbents t flly fntin as effetive dentaminants, t bth srb agent frm srfaes and t qikly reat with them t mplete the dentaminatin. It is primarily de t the rather nsistent panel test reslts arss the srbent andidates that VX panel testing was nt dne; rather, time and fnds were sed t d the additinal reativity testing fr the send bath f srbent andidates. Regarding the reslts f Davis et al., 4 the A-200 srbent was able t ahieve 94.9% remval f HD frm their CARC test panels. This high vale is ertainly de, at least in part, t the zer agent dwell time emplyed, i.e.. the HD did nt have a hane t penetrate/srb int the CARC paint. Hwever, anther ntribting fatr ld be the tre HD resistane f the atal CARC paint emplyed as the resistane f different CARC lts t HD penetratin/sftening varies widely. Therefre, fr CARC panel testing, in partilar, it is imprtant t always emply a ntrl dentaminant s that the relative effetiveness f dentaminates an be determined with respet t the ntrl, rather than attempting t rely slely n abslte dentaminatin levels btained by experimental methds emplying different agent dwell times and/r CARC srfaes f varying pedigree. 4. CNCLSINS The reativity testing revealed that nti:, by far, pssesses the fastest reatin with VX (half-life <2 min) f any f the ther andidates and its reatin rate with GD is mparable t that f nmg and FAST-ACT (half-lives f tens f mintes). Hwever, this fast rate is nly seen when nti: is sffiiently hydrated. Hydratin f nti: als inreases the reatin rates f GD and HD. Yet, the HD half-life n hydrated nti: is still n the rder f several hrs, mparable, bt still nearly twie as lng as that f hydrated nafi. Ths, the fll hydratin regime f these tw srbents shld be explred t determine whih atally prvides the best HD reativity. The panel test reslts fr HD and GD did nt enable a lear distintin f the ptential effiay f the srbent andidates as all tended t prvide fr nearly idential remval f HD frm the Chemial Agent Resistant Cating (CARC) panels (VX panel testing was nt dne bease f this). Hwever, fr HD, it did appear that nmg #1, at 69% remval, did nt fntin qite as well as nmg #2 (74%), nti : (75%), nafi (76%), and A-200 (77%). the latter srbents perfrming identially within experimental errr. Fr GD, all the srbents ahieved 87% remval f this agent frm CARC. Finally, regarding partile size and srfae area f the srbents, small partiles tended t prvide fr the fastest GD reatins whereas higher srfae areas and/r larger partile 21

24 sizes tended t favr VX reatin. The reatin f HD was qite insensitive t either partile size r srfae area, tending t nt favr ne ver the ther. Fr srfae dentaminatin f CARC paint, smaller partile sizes, even thse nder 5 rn, did nt signifiantly imprve the remval/reatin/dentaminatin f GD r HD imbedded within the rgh paint srfae. Based n the ability f ntat hazard testing t remve srfae-srbed agent, the CARC paint appeared t pssess a sbstantial srfae-prsity f abt 0.8 /m 2. 22

25 LITERATRE CITED 1. Bartram, P.W.; Wagner, G.W. Dentaminatin f Chemial Warfare Agents sing Ativated Alminm xide..s. Patent 5,689,038, Nv. 18, MSDS fr A-200-SiC-1005S; Gild Assiates. Dblin, H. 3. Friday, D.K.; Rssin, J.A.; Fitzgerald, G.; Meams, H. Sizing and Timing Trial Test Reprt fr M295 MITT n Develpment f Srbent fr Immediate Dentaminatin; ECBC- CR-057;.S. Army Edgewd Chemial Bilgial Center: Aberdeen Prving Grnd, MD, 2002; NCLASSIFIED Reprt (AD-B ). 4. Davis, W.G.; Kewan, A.; Ca, T.D.; Spakman, T. Frmal Test Reprt fr the XMI00 Srbent Dentaminatin System (SDS). Dentaminatin Labratry Testing: WDTC- TR ;.S. Army Dgway Prving Grnd: Dgway, T, 2002; NCLASSIFIED Reprt. 5. Klabnde, K.J.; Stark, J.; Kper,.; Mhs, C; Park. D.G.; Deker, S.; Jiang. Y.; Lagadi, I.; Zhang, D. Nanrystals as Stihimetri Reagents with niqe Srfae Chemistry. J. Phys. Chem. 1996, 100, Stark, J.V.; Park, D.G.; Lagadi, 1.; Klabnde, K.J. Nansale Metal xide Partiles/Clsters as Chemial Reagents. niqe Srfae Chemistry n Magnesim xide As Shwn by Enhaned Adsrptin f Aid Gases (Slfr Dixide and Carbn Dixide) and Pressre Dependene. Chem. Mater. 1996, 8, Wagner, G.W.; Bartram, P.W.; Kper,.; Klabnde, K.J. Reatins f VX, GD, and HD with Nansize Mg. J. Phys. Chem. B 1999, 103, Wagner, G.W.; Kper,.B.; Las, E.; Deker, S.; Klabnde, K.J. Reatins f VX, GD, and HD with Nansize Ca: Atatalyti Dhydrhalgnatin f HD..1. Phys. Chem. B 2000, 704, Wagner, G.W.; Prell, L.R.; 'Cnnr, R.J.; Mnavalli, S.; Carries, C.L.; Kapr, P.N.; Klabnde, K.J. Reatins f VX, GB, GD, and HD with Nansize A Frmatin f Alminphsphnates. J. Am. Chem. S. 2001, 123, Bartram, P.W.; Lynn, J.T. Dentaminatin Effiay f FAST-ACT 1 (Phase I, Test Servie Agreement Prjet N. 02I9T); ECBC-TR-277;.S. Army Edgewd Chemial Bilgial Center: Aberdeen Prving Grnd, MD, 2003; NCLASSIFIED Reprt (AD-B ). 1 I. Bartram, P.W.; Lynn, J.T. Dempsitin Kinetis f Chemial Agents n rtm FAST-ACT'" (Phase II, Test Servie Agreement 0219T)', ECBC-TR-302;.S. Army Edgewd 23

26 Chemial Bilgial Center: Aberdeen Prving Grnd, MD, 2003; NCLASSIFIED Reprt (AD-B ). 12. Wagner, G.W.; Prell, L.R.; Srrik, D.C.; Hess, Z.A.; Gehring, D.G.; Hendersn, V.D.; Brikhse, M.D.; Rastgi, V.K.; Tretsky, A.L.; Pfarr, J.W. Develpment f New Den Green : A Hw-T Gide fr the Rapid Dentaminatin f CARC Paint; ECBC- TR-635;.S. Army Edgewd Chemial Bilgial Center: Aberdeen Prving Grnd, MD, 2008; NCLASSIFIED Reprt. 13. Yang, Y.-C; Szafranie, L.L.; Beadry, W.T.; Rhrbagh, D.K.; Prell, L.R.; Samel, J.B. Atatalyti Hydrlysis f V-Type Nerve Agents. J. rg. Chem. 1996, 61, Wagner, G.W.; Chen, Q.; W, Y. Reatins f VX, GD, and HD with Nantblar Titania. J. Phys. Chem. C2008, 7/2, Mastikhin, V.M.; Mdrakvsky, I.L.; Nsv, A.V. 'H MAS Magi Angle Spinning (MAS) Stdies f Hetergenes Catalysts. Prg. Nl. Magn. Resn. Spetrs. 1991,25, Mgilevsky, G.; Chen, Q.; Klkarni, H.; Kleinhammes, A.; Mllins, W.M.; W, Y. Layered Nanstrtres f Delaminated Anatase: Nansheets and Nantbes. J. Phvs. Chem. C2008, 112,

27 APPENDIX A REACTIVITY TEST RAW KINETIC DATA 25

28 fi 3 Q = -a Q a > r3 D B < t- (. " 3 ri 0 DC a* ID m > DC in ri r 1 N E sc sc- > 1/1 m m ri = 0 0 > DC >n T T -r -r rn rn -< 0 a, C3 X J3-1- -t -t NC ^C m sc _ * 5 in r^ DC m m DC f*5 00 m < < <* r- X NC DC ) ^ m ^ 0 DC N s 0 d d ri -r vd DC ri -i r^ ^ r 1 d d d ri "3-' K a *-" ^_, 3 0 DC m sc m ri r«l r*i rj DC V 0 -r 00 r- in N DC g vc - N sc >r, -r C*1 ' in ITi t m ri n ^H ^«J3 /j s CD. _ #. -1- t > -r Tj- N m sc C*1 DC n 00 m CD s 1- p»1 0-1 ^C > r) t*j -r vc t~- N in r--»~^ r- -+ q r~- rn 0 q rn ir, r- x! r<s >ri r-' 0> ' (^i d d d ' r i r r <M 0 d d ri rn -t sd DC rsi <N Q x> a 3 0 E 0 s 0. X w j3 N ^» ri sc ri t-; q 0 r^ r- in N NC IT) ~T n ri d ^ ir, m n r-^ CN ^ sc ~ vc <r «C^ 0 T 0 Tt N < 0 m r- r> ~t q *-* ri NC 0 r- rn q N 0 d d ri rn d ' d! ri r rn *-' ^ C/3. 3 s in vc q 0 q q sc 0 3 E t n N -r sl- ri e E DC d m d C d m m <r, e d m d r- d DC -T -a 3 N TT in ri r I -T» q rn DC q C> q CD q -r DC q 0-} ) CD 0 r ri a! r-' d -r d DC sd ri 0' r~ «d ir>' Tf <> d 'ri >r, d t/j 0 E» DC DC DC r- r- sc vc <- sc >n in >/", i N DC 1 :> 00 DC 00 r^ a, X J 1 < 0 > rn r- r 1 -r r- DC d d d rn 1 i/-! t>- t> -r sd DC d ri r 1 ri fi vc 0 (N 1-^ m «C rn N N r^ d d d i*i >n P~ N > *. 3 rn -r «N 0 q rn r^ fn irl r^ sc- in rsi m" m r N vc ^ r~ sc I"~; r- r~ rn r~; q r^ q N sc in r Tf rn /3 C3 N ^t m m m m ri ri 1 X sd -r r^! rn <N J= «. t*i DC m 00 Tf Tt 00 C") DC T 00 m 00 DC sc 0- m -T. DC m DC n DC 0 t*i Tf s 00 CX> <N rn sc DC q -r _. rsj m in DC N ri -r- in r- DC 1! C*i in r-' N d d d d -^ rsj rn *" d d d d (N rn -+ sc 00 <N ~ * 00 9, C/3 5 a 1 APPENDIX A 26

29 m > r~-,, - - g a m v T <* 0 -rr * rt iri r- ^r a -; - f^ in t^ d ^t 5?^Tr<-ir<-ir-~r~- <N00r^ir^rn0Ct^r^\Ci^>r<-i0^^'^;r~; e ' r3 r^ T3 Q -a = - xi > - p* -= ~- D r~ t-~ ir> r-^ TT ^t TJ-' v r» r- r-» t-~ r-- ( - v s ^ vc ^ (N r V") v ' Tf v > D <N Tf n <N n p ^ C a flj a (N 3-3 < - 3 P S. -n^^p 3 a: r 1 H APPENDIX A 27

30 X\'t«1(MN't -axr-virivivi^- nxtn^- N [7 ~ S a "t Tf 00 N 0_r<-it~~;NCNj > >qmn 0000 CMCM 2 G *I C "5-3 r^it^cmnccmtfcmh l/!,/!0 0. a :~ < ~; \0 ^ ^ < * > r^ N N C"> N N N N M h- - "t IN * > : : : rsi CM' iri- TfCMr^ 'Nr--r--r--NN>/"> N ^ 00 rf ^ v v ^^irix't-h - CM CM ^ "1 *n r- N 2 2 * ve CM' - N Tl" 00 '* ^f N - m W X * ' ' < - CM Q S C d x* > 8-5 N 00 ' X M x n x m - N CN N 22 nvn'cr, 1^*01, inx\ (min) Rn Rn (min) r^nrnncnnc-;_ irjmtj-'dsd^r: N^frCMCMCM ^ N-^-00 Tt t N Tf rnin^l-i^ (N (N ^ CM m N ^ - ' ^ ~ d i in in ii ifl > " i N r-' N "S <N CM r<-> ^ m C i;x«*xiri axdri^i^ri NNi''^-rCMCM C < ^'tn^f^vcn^) : : XflXrnX-m't>X [g CM' WXr^X'tx-v CMririNNCM-^dd CM r- APPENDIX A 28

31 >n m sc in r t^ rf rt 00 in 00 vi iri V «(N TJ- r r r ri (N <N (N Tt -t n ri X S in m CI Cl r r CI 0"! Cl 0 ^r 0 0 s r C r in (N Tt -T 3* en en (N Tt m r~ - fi IT) t^ a (N -r s -T r -1- r- sc C n r m -t 0 i C 1- sc in r- s 00 r<~, in K G~ Tis) CM 0 3 C C7- (N C (N 00 Tt TJ- T* <> sd ri v r-^ CM IT) «n «n IT) -1- Tt Tt Tt C C C r S s Tt in r-~ S S v C Tt s r-~ s sc r 1- ^ rs i TC in C -> CI CI CI re in -> r rc C Tt >n f- M 1- v M (N -r i r -r ^ 00 Cl in t t r CI 1- in r 'C, r- 0 C Ti- r r 1 C C/3 - r- 0C -t -t 1- t -1- w C -t -r C i t ~ d s m t -t- r> t ^ r 00 r <. C 3 Cl r in sc 3 ~~ CI r in r^ Ch r 0 Q I - d a > C a.c eg M i M <J C < -r r- r» i- T sc -r C ^ > in ^C s S m C s IT) IT) -r -r r r Cl CI in re " ~ C 0 s TJ- 0» -t C C sc sc C T :-> r Tt Tt < CN r «; -i- -- > -T m C-l C Tt -r in C 1 r -r «00 r CN in r- 0 TI- CS) Cs) 0 j r r I C r- >n s (N ^t- * <C s ^r <N s r es r C 0 3 C ~ 00 X " in r- 3 in rr vc 1 C r- -r -r s X as C r- sc ^ in i- -t re C rc Cl n Cl C 3s <- r C C 3> CI 3 ri 1- r- 9 <t 3* r r r C in r re r m r- 0 r 1 re r sc Cl -l- Tt Cl r 1 sc s s r r', ^0 n C * m t in ri in CM CJ rc re C re re C -t 00 Tt Tt -T > i- < -r r> 0 in 0 S S r «n r- r in -T C Cl r 'C, vc 1 ~~ ~ ri es r i Cs) C C C C Tt 3 ^ ~~ CN C in p> re -> <_ > Tt Cl fn C Tt <N Cl 0 : re H f- r-~, < 1 r- < APPHNDIX A : i )

32 r» 0 r» ri -T m t ^C DC NC DC N ^r fi 00 rn ri r- N DC NC in rn r 0 r- f*n < r sc DC. DC NC r-~ 00 0 m DC ^ ^ It r i r~ NC 0 r- N r~ 0 r- NC «in m -r Tf r*l m r<l m D n rn 0 > DC r-~ r- r^ ~ NC N in 00 r sc QN r r DC r DC r DC r<", DC m DC 00 fnj in m r q m 0- -r DC 5T ^r «1- N Tt r in p» -r 0 r- r 0 N 3C \ r^, m DC 0 T 0 r- m ' ri ri r -r T NC X e. '/, 1 - N 'T 0 ~~ 1 CN) Cl r Tj- - 3 «'-J r -5 3 e a -5 '5 Q = E3 Q x' > rn 00 ^C NC DC f- sc, ri, sc D 0 r- m ^ N r- - N vc m DC rr 00 N r- 0 D N r DC DC r^ CN r~ 0 -r Tf 3 m - r\ in ~ r ^r N r- N NC NC in m t 1/1 -t -+ -t -f -t m rn m m r<1 0 DC DC t-» sc sc sc sc in,^- NC DC r 0 00 N NC NC m DC C*1 N NC «n DC -1-» T -r 0 rr * <N r r- <n r -T NG r- ' r in 0 r- m >n vc 00 Tt 0 0 "< ri r -t m s DC m in f- * ri <* <N 0 0 ^ ri r T in W) sc DC DC 0 0 r- sc in r~ in 00 in r 0 ri DC sc >n ri r -i- ri ir, r r N N r NC 0- -r DC -1- DC -t 00 r in r- 0 D m in DC 3 Cl in r- N rn 0 ~ in 0 r rn DC sc 0 0 DC DC m T in N ^ r- 0 r-' r m in m 0 m m r-~ 1- r~- in in in * rr\ r*i Cl r\ Cl " 00 0 r NC C 0- -r X 3: X -t 00 r in DC S -r C >r, DC 0 r\ in r- 0 TT ^~ 0 0 a rn rn B < -1= 3 «Q C < _ 00 r-~ < >r, -» r 0 DC DC ri -t- 0 n D NC -r 00 0 vc NC * DC ri rf r- r- r r-«0 ri ri < -f 0 t^- -r t*l ri 1 - DC 0 DC rn C t s sc IT) m r -r ri CN) ri DC X sc r- ^C sc r Cl -* N -t «T ^ sc NC DC m DC q en 00 in 00 N t Q\ m vc N 0 -t N r T}- sc C"» 0* ^ r 0 <S n «P- N 0 m -T r- N T r "* 0 0 " - ri n r ^C DC, /, 1 - N ' 1 CN r in rn r~ DC -t DC -r n vc m Cl 0 m 00 r fn 0* NC ri ri in 00 r r- N NC 3 in r DC DC vc in r- 00 ri -f DC 0 m r-- <r, N m 00 r-~ p-- ^ sc -+ r ri ri <; DC DC p>- NC < in t i-', r CN 00 r DC r a: r DC r 00 r DC r DC m DC sc vc N N N r in N DC 0- N ri > m CN DC m t ri m in s DC 0 vc Cl in 00 0 ~~ ri ri r -r -T N r» DC N < ', CN Cl r in f- ri H < 1- ir, < - APPENDIX A 30

33 en Tt N S r N Tt 3 r--' Tf ' d N 3 in IT) Tt -r m en en r«"> <N rs D 3 '/-, r- i N Tf S 00 3 Tf v * en N 3 -f 3 en N TJ- N in r- 3 rs en s 3 en >/-, r- N en n 3 3 <N en -T in r~- " - in m rs -r r<~, >n r-- 3 CI n -r rs V 3 C 3 J*. m r r*i C in m in i 3 r- I s - 3- ** r- -T n N >r, >n t *T t rr m, m m en <N N Tf N Tfr rn t r- a< en -rf r i rs rs NC > 3 N n r i in - en r- rs en n yz T, 3 en vc 3 m r 3 3 IT en en en in '/, -r en en rs n ri s 3 T i en d 3 T 3 3 *T 3 C rs t 3 in r- 3 C <N en en in ~ i t 3 > rs <- r i 1- rs 3 (*N Q - d a P t N r- m >: r n r~- > CI -1- C 1- r- Tf -* t- -r T en en (N r i - r- in n rs en rs (N " C 00 C r*i 00 en >; en 3* n-i r m en m m Tf 3 -T ^ 3 3 <N en en r i rj m in C ri i- r\ - 3 m -T 3 rj <^l r*i en -i- 3 3 i r\ I-I en r -t in 3 C S ri in r^ N rs rs E in f") CN in > in <s ri i r- r- _ ^. 3 N C «n -t m ^ N 3> in t r I r- r- r- r- r- sc in 'A, in in in -r 1- -T -T -r r 3-1- in en 3 r I r»i 3 s ~ en in r rs rs rs C 1 ed Q rs _ 3 ry T, C 2 80 in in r i Tf r» N C 3 r- C N r*i in r- ^^ t in en t SL r- ri m m in in m in m 3* - r*i in -t in r-~ > 3 en 3 3 r i ~ S ri T sc m m r- 3 rs C -r in 3 en 3 rs -si- rs < J r3 s < APPENDIX A 31

34 Blank 32

35 APPENDIX B REACTIVITY TEST SELECT MAS NMR SPECTRA 33

36 APPENDIX B 34 00

37 d ~) [I -3. T3 DC N r- 3> C a < J2 J3 rs 00» q a g eg * Q 1ZD m '_ it a. «i. ~ ' >"! ~ '3» s «*. - : 0 0 : «=. i_ [" - \ s d L z <H "3 ir. <! <M : *H ' ; m 00 * > i " 1 «H f a :- t C/3 < : «H : C ~H ri DQ :,-j - L 00 APPENDIX B 35

38 60 Z5 J a. a. s. G C- M B rj ed J3 N in CM 60 3 g > " -a C -a «N Q / e CL a >r, a - 'B - -C G 0 g N N <N t JS 00 1 "* 1 ii [ *> i C rj as e 2.2 z I <.5 2^ C3 QQ ^ i APPENDIX B 36

39 i 60 s. Z : PL E a. X r - f- t E E. & ^ ^/j r * C^ rt ^ TD L E- es t *, ; t d F «=> F r-( f_ -= -r. r P CD _ r ' rj L ^ 60 N N E E- «: -i ; - h 1 Q ={ N 3 N CM Fi - a. : a a ~ 2 " ^ ja r - 1 > r /j : < & \ S 0 - => Z CJ w 1 «H C/3 r < L C\J s «H : 08 r * : «-* CJ j "-> j 1, ^* /3 _1 rt -r' r e r p 3 6p - iz APPENDIX B 37

40 r^ sc C i a : a X! =3 00 w >> "Q < s: -exp ak v -J J "5 ^ 00 1^""^ ) J g 1 ] ] j J < < a < : «3 S T3 S J=.4 i fl ^ -C Tf (N <=> z -- v «w. r «H ^t- * <N, ~" 1 <N C3 X - (\J II II II II <> ^J (->. m <T w 1/1 i_ 1320 g zm) 4 X 9W 991 * - t _ H M * added 1 regins ( Q T3 i/~l C <L> m. a. te ft : a. at E 2* 1 - J / - «J J J " «- t 2 - -i ^i 0 = 5-1 X (73 < - f l 4» rft L- L * r > J3 M < * <! Tt < Tf N 30 en s DC <N II II II : -a 7 fl -»< ~ 1 w R spe n time the aii < -^ jj ^ ** r CM 1 - ^ 2 S. (N -, S >, X - V - ^5 C : l ~ Sele tthe i was } * "3 : «H 1 Figre B nmg0# ppm) wh APPENDIX B 38

41 _C C E a Q. <D % C s:s D. > X s> i C >- 1) D Tis D m 2 r- C- <r X SSE'^91 -> J s CN E" IS V * Q -a J= II t-j J 0 s \ II X ^ 1 ^ E t C -- x; m a* -< a. <B? E a 0 - y. V '3 < XI y; 0 C p. CJ i y; CJ j s y.. J= ^ ' 2 _ z 5 C ' < a S < a CJ >> -3 4-* C 0 _ - J= * ' X -C 22 a ij a 2 LZ a APPENDIX B 39

42 en = 1 0 n H n -N * r5 r % G X 2 Z3 N 7) *0 J a D t r <M I «D -C = s. f 60 d N < ~~ f) 1 s -a /". a a * -a B C3 0 C * Q B = 43 _i * ~-*- m E, N X '3 **s *< X) C C3 '5b C -^ ex d [A 04 a. S ii z Gfl < 2 eel C 0 -C «T *- -^ z _C Cfl y. r--' CC C 43 s 3 a C/3 tz _ APPENDIX B 40

43 J5 J l J a Q. r3 C ^r -r fn n d r3 r~ t n CM r»» E ^ t g ed * Q - 6 a -3 el "5 r <* C _ t -a z g en - < B «r re «'"5 - S 32 C/3 JL 2 CQ < C/3 LZ. APPENDIX B 41

44 43 "" B1- J J3 00 e»< y. : e : a r3 I "f Sij r^ m -\ 1/1 CD : ~ d a - C3 ed : «0 /N <C - _ C3 -- : w J3 -r. - a - C\J : ** ' C ': a -T 0» 43 ; «-4 ** "t ^d (N : => -. s d : «H II II II -a *t> -+-> -4> eg * Q = - =s. ITi : E D. : a I ) / = J mj y ea _3 ) 3 ^ ^ tra bt imes. " t C n. C/5 C i a - Z T3 :»* - CNJ I -4 (0 3 CMAS indiate C3 2 < 4_ JC 43 : ~ <<* N rf - (0 #<N <J "^ :»H ^t E- <N - C3 C < II II II -*< +-* <> e hi Fig FAS APPENDIX B 42

45 E a Q. 0 C- X ed M n C- C 09 s DC C d a a a a. a. B 0 P l ^ Z. C3 < T3 ^^ - '-5 *- - "3 C «N <D i 3 APPENDIX B 43

46 bfi Q. Q. -a --» Q, I M m a r3 y. M r* a -*i rz Q a s a. w - a. a i- - '5 «-C _/" ~ e» 0 E ~- C3 B»* ^ X 0 a z 00 -* < D- _g fi «^ _ *< r3 " e C/3 > 0.!, * 5 < 5 5 APPENDIX B 44

47 B 60 r. 03 r- r\ -3 S r3 50 r I ea Q APPENDIX B 45

48 XI D a a. -a 09 a I '3 n >r. -a e i as 1/3 111 D a a n Q 3 ; E 0 a. V- 1 Q. -E re x => _ P - C\J 5 : i s ~ *H ^ e C\J Z yi re " - m < ^ -a. v _ 1 re.-. <=> -4* ~; - L ' ID y: -5 _ r^ m ^ «r - C p 50 b s - B APPENDIX B 46

49 0 m.. *> '_ Q. a " - 00 : i "3 *--,13 2 w a CJ ta s. e " r C/5 < <=> 2 r3 ~ L-. (D v:.s «> ^~ f-h -r r3 - ~~ r i F ffl «[ 0 3 Cfi Cfi 2 APPENDIX B 47

50 f- G a a. a y. 0 a, C ~> in J=. s.. m eg. * & *- r~- r*"i m i. >» d r m " m '_j. in -3 Q 0 -J : a - a. L- a «=> '?Z. «H X - 0 rs C3 i - 0 CM s. -> CM vt 2 : 0 7- s < B. C C/j " in C 2,0 a. - 0 r ^ ^j la z : y? «'-a r m VI B ^ PQ a>. m i 3 C3 n \Z % APPENDIX B 48

51 J3 s xi y. 0 D. a M r-- m n d C - =<J F= 2 I 3 g Q a a.,g -a B -C 7Z a a: 2 ' ft- C ^ t SB 3 C. P< -. APPENDIXB 49

52 50 E Q. a v. 6 X C3 S B re J2 P B n -a -a re APPENDIX B 50

53 M s Q. Q. - m 3 B rz s. > s d -a X > a Q. -C a. 1/3 z.= < Q C3 _ 0) Jn % a ( 5 ad -S QQ -C 3 M. Pg APPENDIX B 51

54 J3 60 Q. Q. r, x i '3 60 T3 <"5 d 60 6 g ~ a X > \j _g 'eg.c a> ir> z < a. ~ IS -5 0) /3-02) * g. APPENDIX B 52

55 "3 I Q. D. B9 C x t '3 -r sc n a a i-«e _ C5 5 -a -a -a a X > I-. a. Q. t/1 -- a: z a. g L > <L) C d H r*i =C = 3 S M _' APPENDIX B 53

56 a. Q. I J-. g I '«00 ri d -* 00 I a > =*. m a -a B ^ "»H CM "\ a 0 - spe times aj NM ati ^. n C <L> J ~ ^ 'PMA ated r s m ' $ ~y w tj - ^C 4) 43 \ ^ C 43 t i r * w ^ I l-h / 1, <N rsf C g 3 5* II ( -<-> < 00 '. % APPENDIX B 54

57 H S-m., -E a "C ^-^ '-> 0 1 s. A X - li- ra _ - Sfj Z. - _ * 3 TD : n ^^, «_ - * ~ X - v. _ in «W). _ n.. r*i < 1 r^ ~ - ed I el L X > -1 < v. E in D- r»i.i -> t/2 r3 ts r\ r- CC ~ 3 00 fn tz =tt APPENDIX B 55

58 b C s^ E Cfl a. a 1 Ix => > I (SI a = r> i «3 y. T Q LT> i<j IT> f^ -a 6 a. Q. ^H C > - 5. a B r3 *3 y EM QL, y. E C\J Qd 7 C z r/i ed < i«*t s a _ 3 t*\ in 4t < B I- Ji > C/5 JZ +J m rs ts % 3 CJJ 5 S LJ_ B APPENDIX B 56

59 60 Q. D. v. C s in *-( r-» -T r I = CSI C d 50 ^r rs s g a a - X > Q. Q. 0 r\j n in r s e/5 Efl 2 < «- "^- d> a- 3 Pi 73 JL>.5 C =tt 3 S. C APPENDIX B 57

60 ^ a -r. C Q. I '5 5/J -r «n ri C) T3 C a B &l a* b -3 ed X > I -5 J 0 Q. S pi -H <* r- Z g s a f 8 m a. ^ T3 C M s r- <N CQ < 3 C/3 CD.SP<. H, APPENDIX B 58

61 60 I s. _ in 60 - V m 2 ~ L CD X > I "3 ri d \ w t/5 fm a Ji >- P m 8«Qi '5 K Z «</3 "g < 3 s.a *? **i ** 0) J= _ «-" «J «^ rs s H CQ < Bh P< LZ. APPENDIX B 59

62 Blank 60

63 APPENDIX C PANEL TEST DATA 61

64 PANEL TEST DATA Table CE Panel Test Data fr the Dentaminatin f VX, GE, and HD n CARC Panels by Candidate Srbents. HD(16//Ladde, six re pliates) GD (20 //L adde, six re pliates) Srbent Cntat Residal Ttal Cntat Residal Ttal (ML) (ML) C«L) % Den (h) (/'L) w % Den nmg#l El nmg# nti # nal S A N Den Cntrl APPENDIX C 62