'~·~:, z --I- - · ·; ii~l~L~ 5 1 r ·~ \1 ,* ~"'~: 'l~~tqj7P:~ -r ~· r " 1 rr I ~ c~ti F$~~t 91 ;6 '?.!,r ;>i ~I B 891a i e P r~en a(U 851 i~·i~tR·~~Yd !bl ~iP ~)i: tWf La~i~ ·iS3~~ Y· rZ C L; " d~ " t· ry~;~e ~· 1~1 a~t =~'·sa·. 8~:t .fJ; ,, tSk; r(:n tl ~5h mrrul uo nowcrs rmrrm '": ·" !1!·4~· ~rrrl 4~ L, 111 1 hi 111 raE rronrn or roUoCo a ;f u·v c i, bt~k~ Lltrre ~, 115 I~ Zl Yllrl I! SwLlaltlhk~, dtl '~t-~a~P P~ LIP\:I Ft ;"p~ .r u· I · #a ~b:g' 6( ·: 81 ·' r :·i :ia ~· .~4 44 d·;' s' d ..,1 s· ·,· ;1· ,d-W i ~i~ tr~l ~~e*Tf'ry g~g ,, 1~ i,, 5?-.rZ:y·;ib ud ~· 1~1:~~~1~1 Y~j *s~'~lq~·x. II ··-:r~ic~··~~· ·5) ·'~I -: C .ii ~· I , : ~I I· si': I L" : ·· : 4~P~i ~r"~~ ii I n ~·4i ~~!· ·. ,~~~-ss ~· ·~ - · ::7p ~!~?· ·I ~·I~· i 1~· -1: ~B ~~f~Y .. ~ :· ;· ;· ,, ir: ·· c~ i"' ~:.~ ...'"~JY· h? : ·' '" '411" $~;· ~ 1 '' ·' ·i.·11~ Y-~ w' i 'c~ .+~~\ :4 ·· O LJ 9 ClibPDF - v~~fastio.soni Peselren Report no, 14; PPyHI·JI. IMPERIAL TOBACCO PRODUCTS LIMITED RESEARCH LABOR9TORY HONTPLEL THE REOUCING PROPERTY OF TOBACCO SMOKE 2, The Infiuace of SpC~inp Yeiicle, With ParttculIt Refennn to the Ple4 AuVlor: RI HI Bil~moria Pmjecf He, F6256 ISIU13 BY: Or, I, R, Smith GATE ISSB; nlY 11 1914 OISTRIeu~IO% 13, Or, D, i, Fclton Cop~ no, i, Lfbrly 2, nr, a, n, Gibb 14, Or, F, Harlap 3, Mr, R, 5, Ylde 15, Dr, I, Y, HughcS 4, Or, i, A, Smith 16, Or, R, A, Sanford 5. nr. 5, n, tmdlirh II, Or, 5.4, Sanford ~~ Or. H. H, Bllfm#ril Is, nr, R, C, lcnolls 1. Or, 5. J, GnM 19, A, R. C, Ilchollr 8, Dr. 5, J, Gntn 20, nr, E, a. Fnislcaen g. Dr, S, J, Green 21, Rrs, J, Johnrwn 10, 0r, 5. J, Cnen 22, Ilr, R, F, El Naggar ii, Dr, 5, J, Green 23, Rr, R, L, Rfce 12, Dr, O, 6, Fclton 24, Mr, H, P, Sene~lle Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 SUIWUIY A detailed investigation of pipe go~ing waJ uncrtwen to elucidate wny this pat of smdting produced condensates of low reducing activity, pipe toPaccor smdred in cigarette tubes gave nducing activities ~is· tinctly laer than those obtained for flue·cund t0hleeol but tne values were still hi~ct than those e~tdned in pine Iw~ing. In pipe IR~kinp, using both flw· and air·cund tooaccol after initial high specific nducing activities (j·10 minutes If smotinp), then was a dmp in specific activity as the duration of smoking iocnased, The specific activities tcmardr the end of ranking uen very lo~~ The aecffsing specific activities panlleled thl folmatia of water, No reducing activity was topped by the water accumulating in the pipe, but a considerable ~mP~at of activity was trapped by the ~nsmoted tobacco, Unlil;e cigarette and cigarillo smo~ing, the trapper activity In cigar and pipe smolring was sufficient to significantly alter specific activity, but still much too laJ to give the large total activities Ifained in eigantte ad cigarillo smoking. In all vie other tnne modes of sn~~ng, via,, cigarette, cigarillo M~ cigar, vlcn rll no change in Iledfic activity with increase In duration of sPo:ing (or change in pUtt length)l there differences in reducing activities of Ilao~ing products may be of bf QlOgi ELI d jpl fi cancel C: I i I; PDF -!::!!::!!::!.f3 StlC.i: 0111 ·1· iNTRDOUETION One of the main oojectives of our laboratory is the modification of yield and chemical conpositlcn of tlacco snmke with the ultilMre aim of Identl· fying aPking Irdrerials of Icw biological letivity. We have found that monitoring me reducing proDerty of tobacco smoke is an ertrwly sia~le way of studying sucn modifications or the chemical cwpositron of spolu and have ~aed this property extensively (1,21, AS part of these studies,we have already sharn tnat d r·cund toDlccos, IUO 15 tnose used in we manufacture of cigars and pipe tobaccos, when s~oted in the form of cigars or in stainless steel pipes, gave condensates that were muCh ]cwer in d~chloropi~enolindopnenol·redueing activity than condensates ootained Py smoking Canadian flue·cund cigarettes (1). Huever, we found that tnrr difference between ait· and flue-cured tobaccos is not Is marked when these are ground and smoked in cigarette tuber, Also, some earlier preliminary studies hid suggested that cigar filler tobacco, when crushed by hand and smoked in a stainless steel pipe, gave i condensate with such a low OCIP·reducing activity a to be barely detectable under the conditions Of our assay. mere results suggested an inportmt role for the smoking vehicle in generating DCIP·R~ueing activity. Consequently, a systematic examination of different tobacco types as well a modes of ~ll;ing was undertaken to determine what role these played In the generatioo of reducing activity of smoke and the nruits obtained are reported herein, Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 ·2· InkiiR1KS ~3 Hi~iOM Sn3Hng Procedures Standard rpoi~ing procedure · 35 nl. puffs of 2·rccond duration taken every dnute in toe care of ciqanttrr, cigarillos and cigarsl or ta~m every 10 leccom in the pre of piper · win tleployed, Otffant typer of natural tobaccos rm3ted in ItainLs steel piper, were in a granulated fOlPI (3j. The stainless steel P(PJ "" faPricatad with the ran hole and SKm dipli0nl I t~ briar piles ~sed ngularly by pipe rpni:ing panels in the Ilbwatoy [4j. In contrast to briar pi pr, there a easy to clean ant R·~ae, The condensates were collected and r~P~e solutions prepand a descriscd previously [1), tn this report vet TIM referr to total partlculare aatter collected on Qa~ridg pads, pry isH is Itcinl8 froll wet iPn by drling ever LW or CaCIZ in an evacuated desiaafor tept at 4'C, Redued on of di dloro9nenoH ndoobenol iDe procedure follwd has been ~eseribed earlier (1), RESULTS AW ODCUSSION Uhi k wt had nPokFd lip, flurcured ed feraPnted tOblcCW in dgantte t~ba, a well at pip tobreol in pips, and foad ~l~illemt diffcnnar between tnra, re lad never saed pine tobaccos in cipntte tube, Consequently, re selected two cornercidly available pine tobaccos, vi2,, Old port ind [oafort, Id tnpird these in dgmtte t~er, The ndudng ~ct~vfder at condenratos frpmtherctobaeeor an refori~dlnUle f, Since there pipe tobaccos an cut to aoout 20 cuts per inch, we included a grade of flp·eund tobacco, cut Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 as aaove, as control, Fnwo Vr results c~talned, It will be seen that even tno;gn there pipe to~am give rmoke with distinctly Irwer total aJ well as specific OCIP·noufing activities, the valuer an still siaificMfly nigher tnan those of around 1 obtained in pipe smoking (1) suggesting once again, an ingortdnt role for the vehicle in which tobacco is smoked, The loJ DCIP· reducing values obtained when these pipe tobaccos are smoked In cigarette form, are not surprising when it is considered that tney an blends of both fiw· and air-cured tobaccos towhich rignfffcwt amolmts of additives such as glycerot and ca~olax an added, In the we of Old Port, wnirh is a Dutch type pipe tobacco, the proe#sinp calls for a step called Upiugging" in which the tobacco blend Is held overnight wder a pnssuff (hydrautlc) of about 2,000 p.s,i,, It my be nentioned hen that a ridllr "plugging" of the fluc·cund taoacco had to be carried out before if could be cut to 20 c,p,i, a a laPortory scale, The specific DCIP·reducing activity of this fluc~cured tcaacco appem to be later than is generally obtained for such a tobacco. This loner vain for flue· cund tobacco al#1g with the luer value obtained for Old Port than for Comfort, which is not plugged before cutting, suggest Oat WplugPing" itself involves d~mger wcich an nflected In the spedfic ndueing activity of sm~e, end along wttn the role of additives such a glycerol,nerit further investigation, Nextl in order to determine the role of the pips In producing reducing activity of ~ptC, flUC.CU~d, burleY ad cigar tobaccos wen smdted for diffennt lengths of tin in piper ad the TPn's collected a CJridge pads, The reducing activities of there tars'nen letenined and fmm the Rsultr oresented in Table 2 it will be sea that specific DCIP·ndudng activity dropped sharply with incfase in smoking time, All fhne tobaccos shoved tnis marked deenae Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 ·4· in rgecific reducing activity indicating Mat pipe snPking does Indeed give a tar of iu reducing activity as found earlier. however, froP TP~e 2 it will he seen Mat Me specific reducing activities of the early TPH lasples obdne~ flo~ flue·cwd tooacco wen sch higher than Vie early laapier f~ cigar and buriey tobaccos, After Be initial hilyler activity, all Mne tooaccos, Mljstently gave very i(nl specific dbivlHer, LlnF aDDunts Of I/~fUre Iccurlate and Mese valuer would even he L~r if wet mipnp of IPM were used to calculate specific activity, a~ De other had, no such chanp in Specific nducinp activity with Imiinp tin II observed In dr tee of cigarillo, cigar and cigantte r~P~ing. Hor das plistun accululdte the way it doll in pie laing, in my pi these pthtr nodes of Ipa~inp, hrultr potdned in tiginttl, ci~rillo (nd cigs r.iinp in ilbtnt~d it iigun i. We wondered wncther Me decreasing specific activities with increasing rwkiog tin recoMed in pin Imo~ing were a to my Lap! in the dclieal nature of mn as puming pmlnssel in the piper or due to increased trapping of reducing rubltances by the water oFuulatlbg in the pie and m Mr M~uraea to~leo, To carry out Mis study, fluc·~un~ tmdcco was r~i~ed for different lengths Of file In Me pipe, It MI end of uOld the unr~ed to~wro and Ve Qlidpe pad Ccnlaining me TPW lm extracted separately using I: ethanpl, and h pipe rinsed out aing the san solvent, There extracts were then exunined for their centcnt of reducing activity, Corresponding ImounC of fresh tOlao (egual in weight to the residual uisaoked tobacco in Me piper served as ~mtroB. Yhen there la~t~ pt fmh tPb~r~o In r~traeted'uring 95: ethmol, Me extracts do not shot My reducing activity, em8rning that the activity tripped on the unrald toblco In Me pip was generated during Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 ·5· )ir rnpl:ing, the results cbtained in a typical pipe leoking e~~rinent an I~IMtited in Table 3, Fnn this tile it will be seen that pip rinses It all timer failed to shcw any nducing activity, however, it will be seen that a considerable aalmt of nducing activity was trapped by the unraoted tmaceo in the piper and if Me adds this amount of activity to the activity pp~ained for toe TPM on the pad, the specific activities for the TPN'I are at le~st as ni~ as those obtained for flue-cund tobacco rmobd in ciganue form, but the total activities an still very 1GII Ilhen trapped reducing activity is included and Specific activities Ire expnssed as "units" pr gram toPacco sPI~L~ed, then Mn again pipe t~oie appea~s to 81 similar to cigarette spoicc, and both fnue an a~edly lwtthan cigar uld cigarillo Jmc~L;e, In no ooersade of Ino~ing jcisanrte, cigarillo or cigar) doer the trapped nducing activity elrtribute significantly enough to change the specific activity so w~l;edly (sec iaote I), In cigar rwkiog tbe activity trapped in the cigar butt Is about equal to that collected on the pad, but the total Of there two still does not rrpnrcnt an appnciable activity so ar to bmge the specific activity to My extent I It doer in the care of pipe lao~ingl For etnparative purpwct, riglffttc, cigarillo and cigar butts and asn were collected Md extracted, along with TPM f~Pm these, using 95: chanol, Tne nsulfs obtained an lu~marirad in Table a, That tne nducfng activity defected in the butts of there rPlo~ing vehicles was generated during ~lw~ing, was ern· frma by edndinp approprilte sectiar of tobacco rod of equal Icnglh to the bugs, cut off from unsn~l~ed cigantfes, cigars or dg~rillol~ The extracts did not Show any reducing actlvlty~ Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 ·6· Fra all me expericntr, It is evident that the specific activities of nine, cigar an ripJilo rP~e an indeed Iru ad mit filtration cf~eN account for tne 1~ rpecific activities only in Me case of pipe suing. tne decreasing specific activities in dr case of pipe suing aW be due to n· pyroipir ocfjning to a greater extent In thir DJde of lalnp the in the slralinp of the cigarette or dgarillP, H(liever, If aay be stated that no lup de~na~~ng Ipcdfic eetivitiel an obtained in cigar Istiag In whid case also thm it conribrlole le~ua~lltion of reducing activity on the b~ttl relative to total MtjyitY~ Thus, I far a total activity (lad pld bUtt) is cmcemed, nine liinF is veri similar to cigar rPa~ins ad DoV1 give EmriderPly liver activity than cigarette ad cigarillo Imo~ing. For caventcnce, a n8~1 of all these results is pnrated in Slble 5, in cmclurim, it nq be stated Pat thee results Sh(w that Vie rmoting vehicle das play a Idar role in the delivery of reactive ccmpordr, 16 indicated by OCIP reduction, to a smd~ing individual, there results, a well a soR pnlidnay Studies carried cut in this labcratory (5)1 suggest Mat ~drd dlMEer an introduced In t0ao which hi been Ypiupped' or to which additives ruch a glyceml, pmpylwF glycol, potYroPylene Glycol md caro#Ec nave p~U~ adder, and that these Onpls an reflected in Me reducing property of the I~d;l~ It is suggested Mat such additives aarit lurther investigation for their de on cigarette tobacco fma the point of view of sue nactivtty ~ xeil a on biological letiviry, Finally, although Me differences In mortality rates between Imterr 01 cigarettes on one hand, and dgan and,or piyr a the otner (6JJ in generally Irapted as being Iv! to diffmne~ in depnt of innalaticn, this rtui~ bat indicated diffenncn m tae ndr Icnirtrl of there products which Ruy be of son? biological Ifyif(canee. Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 ·7· REFERENCES i. M, d. Bliin~ria and n, I, ltbet, Beftr, Tdaitfonch~, 6, 23, 1970. 2, K n. Biliacria, Igrill tobacco products itd,l Mkntreal, hearen Report No, 142, Issued Febnry 26, 1974, i, R, i, Rice and T. R, Yth, t]eltr. iapa~fo~cft, !1 241 1973, jSee I,T,P,I. Res, Report Ho, 137, issued March 23, 1973), a, d, ~, El BgOn I~eriat Tobacco producrs ltd., Reseam Lp.l nontRP, la~ontory Pcport Ib, 70·1, irrmd March 1J, 1969, 5, MI H, Bilimoria, Unpubilrh~d wcrl(, i, C, Haa~nd 13, nom. J, Ar. Yed, Assoc,, ~ 1169, 1294, 1956, 7, R, Ooll and A, B, 111, Brit, Med, J,, 1, 1399, 1964, Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 'IhBtE 1 ICIP·REnUCae Amvrn O~ IIPE mueeos sncltFP n crc~r~ maEs. P, of drp I Ilo, of ~eti~tr TPblcCD T~ ftOn puffs TOEI1 LCtiYitjl Specific 5 eign, per cf~l~, I fru I c4tl~ "Ud~ll plr (pp,, ng TP~ ~lugSad, flur·curcd ilO U f95 5,10 20 c,p,:, Old port 117 12 286 2,16 C~fort 79 1l 285 3,62 It~ Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 'IABLE 2 DeI~·REDUCINC ICfIYmES Or IIR· ~D ~UT,·CURm - moxro n StbI~ f0MCC0 ..~.1. ... .----·----- Ut, af I Wt, of Iwt; of Iracmr DCI~·redueing vtivitp r~3a Y(I drl lace ia leeifie e~ivlr~ (Ilnl~) ~o~cd TPH on "Units" pot ~g~ (8m,) log,) (ng,) drliPg dty ~Pn gc-eurcd - 1-. 0.11 L.Z IJ 1 6,9 10 O,Sf 11,5 11,8 1S 3,4 20 0.80 43,7 20,0 54 1,9 10 1,55 183,2 36,7 80 2,2 b0 2.19 ,2 87 O,b Air-cured cs~ I 0,i0 5,4 4,9 9 2.9 10 0,61 6J 6.0 r2 1,1 20 0,94 41,5 0 7~ 1,9 00 2,00 ,0 5,6 7L 0,2 60 2,60 75,6 80 0,2 Burlev 10 0,25 19,1 8,3 57 1,5 20 0,72 47,3 910 81 O,f 40 1,75 ,7 ·2 81 0.1 60 2.35 ,4 ,9 86 0,4 4 TV Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 FIGW1E 1 PIPE SnaKINGr Ef~CTOF SndKIN6'TIHE ON CIC?S..SYOY~IG: EIIECT of WOK~ TIPE Op tpn I9LD AND REDUIING AC'IIVITY fPM YIELD cap DCIP·RLDVLwt PCtIVITr "1' I t'Cr i" ii idC ia t u ii z > :P 2. r 2*I d r cr "·~'~~1 "\·.. 12 P (1y I / ~ ~ I tPn O to 20 jo cO IO 00 i to 20 30 10 50 60 SlrOWNG TIFE IN FIINUTES WFF NUMBER QbByLO SMQlclwb: FfiECt OF SEloKmd TeE4N OGAREtTE SWKIKG:ERECT OF FMOKI_NC TIYI OU ~9E~Jl rm nilD IHPPD,.RrpuClnLAtIlVITY vEt REDUCIN~ ,DRY ACTIVIM /rm 7r / I mi u r 1 :ur 5 ;IIR1 SP t t 2 ~61 O IDUUY (2~ B I p: u 0 5 10 is 20 22 O 1 c 10 0 PUFF NUMBER PUFF NUkBOI Q (U 0\ U Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 TMIE 1 D~SIRIBUTION DE RmveIE ACErcm ~E~wrm Tp~l PIPE RINSE AND Il~tSEHI~ED TOIMCUI (FI1IE·CURED) IB PIPE S~INC lime of Wt, of Wt, of Wt, of I DeIr-reducina activito ano~inq tobacco Idty f~ per Tool 1 Soecific activi Ind smoked TEH p, seti~ity eoUrEe (p.) bB~) tobacco SPI~H 'kOnitln 'Z]nifsn rooked per me, per 8, (mRl) dtT m tabmcco IIDOM 5 min, ~t! 0,21 3,8 18,1 20 5,2 94 Rinse I I I Nil Nil Sil Un~ao~nd ~oboeco I I I 1 59 UI 277 r0 mio, TPr 0,45 7.8 52 6,7 116 Rinse I I I nl wl Nil UnrPPU tobeceo I I 1 110 14,1 245 20 Pin, 0.73 10,6 14,5 51 4,8 70 Rinse I I I I Hil Wil Nil On~o~Ld robsfeo I 1 110 1 lb,l 150 CO min, m 1,69 13,5 8,0 so 3,7 30 Rinse I I I Nil I111 N11 Un~n~ktd tobacco 1 I I I 71 5,3 12 60 min, TDn 2,09 19,4 9,3 Is 2.5 23 Rinse I I 1 I Nir Nir ·I Nil UPsPoked Loblcco I I 60 3,1 29 100 nin, nle 3,45 212,5 64,9 172 0,8 50 Rinse I I i ) Nil Wil Nil Dnseoked Eobsefo I I I I Nil lil NI1 B C U U Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111 ThaLf 4 D~SBI~IIIQ DCr~-PleP AefIVITT Im'P1( ~ 488 480 8nrr n saaKINc lit, of Wt, of Vt, of lolrcr tobuco ( d~ lo~l IP*ific ~clBft~ ~bl · ,,*p 'Odt~' "Oofto" (B1) 411) tsl*to "Uooto" r~ll la II h~) 10 M tsbleeo rlhd ErWJlt~nS - I~ERS elP 13 RM 1 3,06 1 119,3 1 31,9 1 893 t,l 292 488 I I I I ' Nfl ~1 81 Ltt I I I 1 154 1,3 lo er~~· ~cvam --· ha 92 1,4 U nth Nil Jil 811 lurt II 0,1 7 Cf~~S-~ Im RH 11,41 1 311,0 1 27,3 1 588 1,9 11 Alh I I I I Ntl NiI ' NII Ltt I I I 1 53 0,2 ~( tor voi8hto I11 totll ~ctWtLI ors Ior I ciylttll, cil~t~ o~ ci88riliol, N U W ClibPDF - v~~fastio.soni TA~ I I RRMIRI ~I BES~S ·I I ~~t It~t L11 oi L~I~ eil~rettl eiyrl eiptil~l ~11I ~I I~hic~ I1I1 Iith 119 b (lilh It ~~ ~ of Mlp tpb~ceo ~~~ db do- do- ~: rn· ~a- ~b II r~e~ ~pl· siffe ~ct~it~ Bt~l pen- ~P- ~O· BC ~ol r~~cLI ~cti- IP~td toLe- sysif~e Olc~~ Ipw~iie Ipr~ie co~~lt aen- ~ct~itl Ict~io =:P:~ ~ctWLI tldPckl ~)tc~- rh 1~1 cl~ll to L1Clt t~ fic ~et$it) L~ t~~ bo ot ~LI tLt f~f of of ~ ol ~ ~aPltio~ ol Ililht CIIYa- Ilif~t e·l~alh, ttl~~ tdpt. 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F~X~! ~i~i~l~i a;~·4.:·rJ~I ·~.4'" a y Z~rs·~ ·; ~. ~t'~ "L II i:i:rl·: : ~i ~i~e .1,·,.· ~-·-· ~: · PI~X·~5111 ~'* ~C "` ~s~l:s: *.·.·: ~d.; FIP~W~1:OP· L:E'.:~C l;~u~~~I~'L ?!!t ·*· ,, !~1 .. ·J:··:E: ...: ~ '"i:.P" :ibt~L~j ·J; i~i ·: '~" r ~p~r·r E,e~~ is "· %~ r· :r?· : : ·.: ?1. ~ :rlCs~ i:, %Y~i;%!::~·.·r 3 :J:: r ~·:·r. I~:,~; L·;'11 ·· ··Lli·· *;~-:HVllh~:''~YrT~H1%:;l ,,, '·':· I:: ;; -~··\ I~ h: ,.~ " :'·r ~~;t '' '* -·$ ''· 'a\~if~i~i~B ~1: i 'C~EII: 1· * ·: :: r, ?'. ·~~.. al ~.·s~SP': I~?j~·$ i' ...j I ' * .-r. I S'' ,,:, :., r*rE,lk*~a'' ~. '!'1, ~···~. ~I;'····.' ·'.' '' ~ '''~ ? ~~~~~:~:. ,~ ,Y 1: ':I ·· ·~ ~·.··s-·· · O I~ C\ 'J Cn Clit; PDF -!::!!::!!::!.f3 StlC.i: 0111