Tobacco Documents Online

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B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER S:-:CKE GO.~STIT~TS A.~ Tb~ Pd~I~TIO!~ TO .~UAL~Y ~RISTCL CO.~F~.E~DE APRrr- 195~ I, W, Tt~I~R, DD~CT~R (~ ~Fa~!~H l~/I; & W~L~.~ISON TOBACCO C(ItPCRATIO~!

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER T~B~E OF CONTENTS Page DISCI~SIONI S~ CO~'~TITb'F~'~S AND TH~ KELATION TO QUALITY ......................... 1 - 13 ~troduction • • . . The Physiology of Tobacco Smoke Constituents.. .... 4 The Formation of ~oke ................. Physical ~asure~ents of Tobacco Smoke ......... ii II. A REVI~ CF S(I.~. PER~TI.WE!~ FACTS CO!EEF~NING CH~.~CAL ANALYSIS AI~ QUALITY .................... 14 - 26 III. A~IX Table I. Tobacco Smoke Constituents (Including ~blio~rap~, Thereto)

CONFIDENTIAl. MINNESOTA TOBACCO LITIGATION "~~.,~...~ ~

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER ~. ~. The research oepartments tb~t exist within the tobacco industry are largely ~i~'~~:~ .devoted to such projects as can he Justified within the concept of developing a "~::~'~'~ :~'technolo~ical improvement. An important consideration has been the possibility of i.: )~(~!'.:'~econc~ic advantage to he derived frc~ such a pro~ram. It is within this pattern ! . ' ~i'-' tk~t such ~ork on s~oke constituents has be6n c~nsi~ered in the past. Igithln recent ,: ! irC,~' -~:~ ::.i '.. monthe, he,ever, for those of us ~ho have ~en in the thick of the present contro- ~'~ ~, '~" versy on the health aspect~ of smoki~, another facet of the industry'e interest ~ '~' "~ has become evident that involved also the has been It increasir~ly ~e .~ ~oral rsspor~ibillty, legal necessity and the technologi'c21 importance of a further end more basic ~nderstandin~ o£ the nature of our products. ~ ~illions of are no~ ~In~ s-ant, a~ ~ ~llAo~ more are ~i~ lost t~o~h ~ecreas~ sales l~rEe~ ~ca~o the scient~ic facts are lack~ to ~ck up a d~i~tive statement . regar~i~ the ~t~e of ~ pr~ucts. It ~tters not t~t ~ of o~ oppo~nts ~e largely irrospo~i~e in the~ pu~ic prono~c~ents for they imve capitalized not so ~ch on their scient~ic fi~s ~t on the fa~ t~t we ~re ~-~e~red to meet a cimllo~e. ~ respo~i~ty ~s never more clear, a~ the sit~tlon mere~ tends to emphnsize the ~no~ance of ~intai~ a ~d, obJe~ve outlook Thi~ responsibility is not only to the public the industry serves, but also to ourselves so t~:at ~o, and not the Win~ers~ the Grahams, the Hills and the Dolle~ are the ones who can .~a.~e aauthorlta~ive" statements regardin~ tobacco. Quality, as it has been vieued historically, relates to such taste and factors as mil~ness, body, flavor, aro~, strength, satisfaction and so fo~h. su~ ~ot~l of ti~cse adds up to eajoy~ent of the act end after effects of ~moking.

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER ~. . It i8 perhaps i~possible to delia; q~lity ~ ta~ of ~he ~e~ia~e taste res~e ..v~n ~ ~v t~t includ~ ~so are n~ero~ ~siolo~ical a~ psycholo~cal ~ of an ~efine~ ~g~tude va~i~ ~th the iudivi~'~l a~ tha circ~- 0~o~ the role ~ the cicarette to a person In a ~ht spot ~ith gay ~ic, ~hter~ gaiety, and ~ a~a~e of ~coho~c ~Verage is q~te d~ferent t~t to s~eone ~ssi~ a restf~ eve~ at h~e ~fore the fire ~th a go~ book. Another mental picture we all have is of the student or ~riter stru£gllng - ~;far into the night on a ~ifficult mental probler~, in the course of which he cor~es a surprislng~ larv.e ~-,~ber of cigarettes. ~ether there is one single or a~y co~binstion of specific £n~redients in smoke, that constitutes the c~m~on demon£na- for of smoking satisfaction, strikes me as being highly i~ro~ble. • ~ Quality in ter~s of the c~nplete consumer response is a vest field 8ese~v our serious consideration, if not our aggressive investi~atlon, l~e are bound, however, to a~opt the approach that the initial and the most i~portant appeal of a '""~ cigarette lies in the or~.anoleptic response. Our tools for measurement, crude as '~i they are, are the best we have been able to employ thus far. This is, nevertheless ~ered~y an interin ~eans of dealing uith the problem and we must ever be alert to the " pOssibility that ~e may find a measurable p~siolo~ical or psycholocical response !' that is of equal or even greater significance than taste. The cardiovascular elf acts ~ of nicotine, for example, are well recognized a~d o~ significant ~agnitude ao that £t has been possible in recent years to relate this response to the campnsition of the cigarette and its smoke. There has been Sncreesing evidence of interest on the

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER feel very strongly t~t the tobacco indus, try will in the future be ~hese substances and their specific biological action in the q~mntitiee involved. If we learn that an~ of them are a source of ill-effects we will ~ant to learn also how the methods of manufacture o£ cur products can be modifie~ to eliminate or reduce the~ to tolersble amo~mts. Our knowledge of the qualitative presence of a host of specific chemicals will be of little value until we reduce our technics to a ~uan~i- gative basis and develop our understanding of their physiological s±£nlficanco. Ctu" exploration of tobacco smoke co:~tltuents is only ~mlf t.he b~ttla. Not only do we want to develop our technics for manufzctu~e to brin~ out the good and eliminate the poorer constituents, but our .advancinC toc}~ical information vltinately be aimed at direotlng .breeding studies to the production of such variotie~ with de~ermlnahla~ favorable characteristics. I~e have alrcady seen such developments ta~e ~lace An the case of low r~Lcotina tobacco,, but, unfortunately, it has to date been difficult to deal effectively with other important considerations in developing an othar~r~so satisfactory varLaty. ~sse~ upon s~oki~ tests i~ |~s ~en almost i~possible to assign degrees of poor q"."lity so timt havAn~ ac]rLuved thc objective ~ of low nicotine the breeders are stymied in their attempts to incorporate oth.r ~ desirable characteristics for lack o£ a pard stick. ~: called upon for infer:ration relatl~a to the physiological com~equence of the presence, ~.. " of ~a~ of the smoMe constituents. There is no need for alarm for there is a long r" '~:" ~ietor~r of tho safe and pleasurable use of tobacco and such ill-effects as ~ay be ': ':~/~ associated with ~..~okt~ are of a ~tnor or tra~itory n~ttu'e. ~kOloal science has, oint ~here the well-bein~ of the individual over and " ' ,., above hie ~eneral good health are bain~ given increased consideration. Hsr~v of the • ''~"- • :reporta~ constituents of snake are ~f a nature to lead one to believe they are of physiological si~niflcance. In tlu~ we uill want to develop further knowledge of

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER upper eyelid ~o,~brane of the rabbit. (~dly enough the results using the t~o methods u~re not in accord and the eyelid failed to respond to variations i~ the smoke from cigarettes otherwise s~milar except in r~cotlne content. Since the pr~uction e£ a measurable edema of the eyelid uas shou~ to" be characteristic of oi~eretts smoke, this for~ of irritation appears to be different frc~ that tively observed ~ith human subjects. That t1~e rabbit responded to the subJeotive

('B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER but in a significant but a~aller nercentage the reverse effects are observed. The ~'~:~eonstriction results in ~eaeurable temperature decreeees in the extremities, in- ~reaeed pulse rate and blood l~reesure. These effects appear to ~e ~i~ectly related exclusively to the nicotine content of the smoke az~ take place ~ost.lmmediatel~ so that they can be considered within the range of response sNar to flavor sensations. etber these hono ens eseoo sted , th the of nicotine the h~an syste~ ere to be co~sidsrod favorable or unfevorsble quality factors to the best of n~r knowledge cannot be answered at this tins. Ar~t~ that regard ~ould be gross speculation. ~ can vis~allze reasons £or ta~ a ~ o~e side or the other ~t as in ~ questio~ concer~ ~ e~fects of cigarette ~ke there ~s been f~ too ~ch opi~on a~ too little fact, The possible a~algeeic l~roperties of nicotine an~ also ~ ~a~7 other con- stituents is perhaps ~orth exploring. X know of no ~ork that has been dons along this l~ns but from various observations of the comforting effects of seeks, ~ " strongly suspect that is contains s~ethi~ of this nature. ~la~, if n~.t most, of the other constituents of smoke are un~oubted~ of phTslologicel significance in the c.uantities ~reeento The alkaloids related to niceties have been investigated to a iAnlted extent and bear s~e si~arlt7 tO At. The ne~er tobacco strains that are bein~ promote~ in some quarter8 are higher'in nor-nicotine than nicotine content and some specific P~nowle~e of the consequence of this vould be appropriate at this ti~e. As an appendix ~e have presented

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER Zizt:Ln6 most of the conpounds which have been r~por~ad togather 'trl..th each iaform- tion about theAr taste and phyaiological propertlea as' can be briefly stated. Zn all cases the concentrations are well within the t~xio ll~it and what is lacking frc~a ore" point of viev is the effect of long confirmed absor~on of these materia~ eratlon of sm~e co~tit~nts. It is one of t ~ts at w~ch, ~espectlve of ~i t~t ~s ~en p~ce ~evlo~ ~th respect to ~n~act~e per 80, a de~ee of con~ol can ~ ~erc~ed over ~e c~racter of the ~ke. ~ ~s~ ..... oo~equence of vario~ c~es in leaf c~osi~ion. The trigger to tha process of smoke generation is, of c~se, t~ zone of o~ion. A t~rat~e in the neigh~rhood of ~ is reached (or ~intained) ~ t~ ~e as a co~equence o~ v~ch ~actAca~y a~ of the ~ga~c ~tter not ~io~ vo~t~ized ~ o~ ~a~ or another is b~nsd ~ othe~se de.stied. T~ ~ne not o~y f~shes a p~ion of the am~e co~tituents a~ ~ssi~y tbe ~¢lei for s~osequent ~rticls fo~tion ~t also provides the heat for the ther~l decathlon a~ d~tillation pr~esses t~t take place f~thor do~ the cigarette ~rd the ~uth e~. ~ factors, it is to ~ exacted, enter into the act~l ~ess t~ p~ce ~t~ t~s glo~ area and several qf them wo~d se~ to be p~sic~ st~ct~e of the cone w~ch gover~ the ~th ~ wMch air is ~ra~ ~ to ~o~de the essential ~on for the co~tion process. T~s ~iI dete~ ~t

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER i~"~is a gradual change going fr~ the area of active oxidation in the glowing cons to .that of thermal degraoation. There ~ust, however, be a ae~blance of a boundary defined by the butt end of the glowing section which would provide smm Justifica ticn disc sion of on sis. We can oz~ly speculate on the nature of the reactions ta~ing place in this region. Very probably the carbohydrate ~atter undergoes dehydration and certain portions of the protein ~olecules are brcken off and become incorporated in t~ smoke strea~. The iLl,her hoilin~ resir~ and £atty ~terials ~ay be l~7drolyzed and otherwise cleaved with subsequent oxidation to smaller molecules. Since there ~ be water vapor present at an elevated temperature the possibility that it enters into chemical reaction ~ust ha strongly suspi~ionsd. This is the area in ~hlch the chemical reactions m~t be extremely complex but also it is of such a nature tl~t experinents could probably be designed to reveal the behavior o£ the ~rinus known loaf constituents to this type of process. Undoubtedly, a great deal could be learned if the proger talent is emplvyed to shed so~e light on'~hat is taking Tho temperature of the gas stre~ appears to decrease ~atber rapidl~V once ~t has left the glowing area° The charrin~ that is evident does not extend into the body of the cigarette ~uch beyond the burning end of the cigarette which indicates t~t the temperature falls very rapidly to a point at ~hich its action is essentially llrAite~ to evaporation of the more Volatile constituents. Nicotine has been shown to Underco distillation, degradation, and prohabl~ co~.~tion. Tho behavior of nicotine is, of course, cemplicated bp the fact that it is a base, subject to salt for~tlon, both in the tobacco and in the s~oke, v. a ~ense, ho~eve~ it is typical of a number of leaf and additive constituents of

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(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER tobacco smoke is not ch~ca~ly homogeneouS. Xt Yes also deter~Ined that tha • number of smOke particles is of the order o£ 106 to l~9 per ca. frc~ a 35 .'.,: , ilter two second puff. This work of ~bbs is e~re~ly interesti~ to us at ~o~ & Willia~on ,~ cloy of its ~llcatio~ ~th reseat ~ the ~rfo~ncs of falter tips. PXs resets ~o ~t ~press ~ as bein~ concl~ive a~ certai~ ~e ~ve seen nothi~ "in ~ ~ ~r~ents t~t ~o~d support the ~ev ~t the che~cal com~sltion of. "~ha various sizes of partlc~es is not u~orm. ~uch ~ack of hc~sn~ity, i~ it exists, is to the best of our present knowledge not of .s~ficient ~agnitude to anticipate a selective chemical separation by a mechanical filter. The particulate ~attcr most cartainl'ym~kes up tim bu~k of the smoke and ~ the non-condensibles on a ~ei~ht basis are a very ninor portion ~nd we can visualize, o~y e limited number of specific substances as bein~ present. The nora important components are nitrogen, oxygen, carbon dioxide, carbon monoxide, and a portion of the methyl alcohol~ acetaldabyde, formaldehyde, formic acid, an~ certain low moleuclar weicht nltro~en components that escape condensation on the particles.

U(]NFIDENTIAL-MINNI~'SOTA TOBACCO LITIGATION

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(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER axperi~nts reported bear little relat£onahip one to another add serve only to ... indicate an order of magnitude of the various c~r~tituenta. This smoke, made up of products, of inc~nplete cc~bustion, pyrol~V~is and volatilization of tobacco, is largely in the form of liquid l~rtioles containing . dissolved or dispersed solid matter. When condensed it has a dark color a~d a salve like consistency. In normal smokir~ without i~halation sc~eth~ i~ the ~elgh~o~- hood of 5 to 15% of this particulate matter cor~enses i~ %he o~'al cavity. The . a~ou~t retained ~y ~he i~divi~u~l increases sharply with i~c~eaaed i~lalzlo~ a~A is reported to reach a ~ of al~ost 100%. The whole apprnsch to tobacco smoke analysis has taken a variety of forms. .. The ~ifficulties of deali~ with a mixture of several hundred cc~pounds have been =~ ' " ' trenendous and the results in many cases vague. At the present ti~e nicotine is " . perhaps the single specific compound for which an effective laboratory methnd is ~. ,, available. Others have been devised but these are so ti~e co~su~ and com~lex~ that, as a basis for continuous investigations, they are oflittle value. They have, however, been extremely useful in developing an understandi~ of the quali- tative composition of smoke and have given indication of the order of magnitude of numerous constituents. Xt has been passible in the past to a~criha greater signif- iccnce to tho results of such gross determinstions of which total ~olatile base, total volatile acids, pH, and tars are typical. ~radford and his associates in studies on volatile bases and acids of tohacco '~ smoke obtained the followinE results ~or total nitrogen, nicotine, and total volatile ~ases. The figures are in rag. per liter of smoke.

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER "Zbe volatile bases of smoke consist almost entirely of mtcotir~, a-~onia, an~ a~Ines and account for about hal~ of the total nitrogen. The ammonia is derived "~rom the ori~inal a~onla of ~he tobacco, fr~ pyrolysis of other nitrogenous cc~a- poun~e, and slight ~rolyses ~urin~ dlstillation.~ The presence o~ organic acids in tobacco smoke ~as "also hson adequately demonstrated. N~uberg an~ Burkard have identi~is~ fc~rmic, acetic ar~ butyric acids. Gnhel and KAprlyanov report the identification of formic, acetic an~ propionic sci~s in the distillate of ~estruc~ively distilled tobacco. Bradford and his associates confirued the presence of formic an~ acetic acids. The reeults of their deter~In~tions in m~. per liter of snoke are as ~obacco T~s _T.V,A. as Ace.tic ~cld Formic Acid Bright 7.13 • 1.17 BUrley 6.58 _ 0.72 ~urk~sh 5.50 0.76 Blend 6.47 0,9~ ~rsom a~ lkag report values of 0.50 rag. ~er cigarette for £orz~.c acid an~ 1.70 m~. per cigarette for" other volatile acids. They also indicate benzoic aci~ is present in trace a~ounta. The ratio of total volatile acids to total volatile baeee has been inveeti- gate~ thoroughly in an attempt tO ef£ect correlation ~lth s~oking quality. It has been ~ound that cigarette tobacco that yiel6s an alkaline smoke is of poor qUality

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER that qu~l.ty ~nproves ~th increasin~ acidity. ~Arley tobacco is high in volatile nitroEenous constituents an8 ash ~h~le low in reducin~ sugars. E~'ight tobacco, on the other hand, is relatively high in reducin~ sugars an8 low in nitrogen ar~ ash. Turkish tobacco is of intermediate composition. In blending these various types of tobacco, tobacco ccnpanles attempt to pro~uce a cigarette uhich ~ have a suitable acid-base ratio in its smoke. The ratio of total volatile aci~ to total volatile bases is related to the qunntity of s~ars and the naturs!ly occurring volatile bases ar~ other nitrogen bearin~ components in th~ tobacco. These may he the natural reducing sugars of the leaf, or added Elucose, invert sugar, or sucrose. While st~ars contribute somewhat to the quantity of acids present and increase the proportion of formic acid, theirI principal function is inhibiting base formation and this reducin~ alkalinity. The added sugar seems to reduce the amount of ammonia produced during combustion and to a lesser e~tent reduce the amount of nicotine transferred to the "main strew". Tb~ alkaline tobaccos, houever, are rich/~ aroma, ~r~ich er~-nces smoke quality ~i~ich is a fact to ba taken into account in its relationahi'p to the volatile acid to volatile base ratio. Any discussion of the acids and baae.s, of tobacco smoke necessarily must include nicotine ~Lch in a sense .~as a multiple role in tobacco ~herAistry, It influences the acid base ratio and ~s other properties entirely unrel~ted to its alP~!inity. Such smoke that can be characterized ~/ its acidic nat~re ~ill, in general, tend to ~ve a smaller percentage of the tobacco nicotine in the "main stream" smoke. The alkaline smoke such as derived fr~ ~urlcy tobacco will not o~/y contain a hi~hsr percentage of the tobacco nicotine in the snake but o.u/te naturally a latter por~ion of it wit.1 ba in the free state. This fact would appear

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER to have a distinct bearin~ on the character o~ cigarette s~.~oke, ~ut an additioncl factor which has been suggested is the flavor and aroma which are characteristic of the basic components other than nicotine in the smoke. Zn other ~ords the acidity reduces the irritating properties of the smoke but unfortunatel~v in so doing a portion of the aroma and taste is lost. ~r~dford, et.al,, have summarized thei~ vie~s on the i~portance of the bases as follo~s! "~ghen smoke is alkaline or in too high concentration, the bases act as irritants... Yet, without a sufficient a~ount of bases, smoke is flat and lackln~ in character. Nicotine and av~cr~ia are not inter- changeable in the base fraction. As the proportion of nicotine ~-ncreasss from the l~er extreme, the smoke (weak an~ sone~hat irritatir~) becomes s~othQr and more satisfying; as the other extreme is spprceched it becomes heady end deficient in flavor a~ sensibly more acid than would be i~icated by the acid-base ratio. These changes may be mas!~.ed, however, by added flavor, or, as is the case of the Turkish cigarette, by the natural aromatics of the tobacco plant. The acid type of smoke, although less noticeable than either excessive or free bases, is described as harsh or sharp. Hoseley, ~krlan and Ha~mer have summarized their viers on the subject as follo~m! sC~nd quality of ta~rley tobacco is related, in general, to a low content o£ total volatile bases, a high ratio of nicotine to total volatile bases, and a reasonably high ~ineral content in the tobacCO. For total volatile base At is necessary to set a ~irAL~n~ value as well as a maximum. E~tremely low bases indicate over~ipeness, chaffiness, and a. general lack of character. Aside from the deficisnc~ of ar~ in such tobaccos, they sometimes carry an tmpleasent, earth~ taste. the data for total volatile bases are of value prinmri~ as a measure of strength, the ratio of nicntine to total volatile bases bears a very consi|tent relationship. to ~he quality of the smoke. This term incorporates such factors as s~oothness and

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER That the acid-base ratio is not the cc~plete answer to a pleasant smoke was evident frc~ the fact that a heat-treated hurley cigarette which is a very poor smoke possessed the sa~e ratio as a popular d~eetin brand. Weight of the cigarette a~d moistore content are also considered important in modifying the acid-base ratio. Nitrogen in the tobacco supplies the greater portion, if not all, of the alkaline constituents in the smoke and it is interesting to note the various forms over quartz at 570°. ~k~t of the non-nicotine bases are phys$ologi~ally much less important than nicotine, although, s~e, particularly m~osn~Mne, eocratlne and ~yridyl ethyl ketone, are important for the aroma. l~role also has been identified in tobacco smoke; but it has not been established that this results frc~ the pyrolysis of nicotine. Frc~n reported 0.2 0.8 ~. per cigarette. It appears that the same conditions of combustion that nicotine content favor ~rrole. ~eCampos, in a study of cigar smoke, fou~ pyrrole

• ~B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER in the Smoke of leaves containing no nicotine. :. ' In a repor~ to Brown & Williamson in 1936, Fo~ter D. Snell reported a 0.217~ '~, ~- "'- pyridius with six puffs, 0.223% with eight puff~, 0.050% ~ with six puffs and ' • ~ 0.058% th eight tt~iDg the viCER0~ filter tip then used. Without filter there : . i ~ 0.~s~ m~idine and 0.~ a~nia with eL ~fe, 0.19~ ~rlene and 0.0~ ~ : ammonia .~ith eight. It was concluded that ~-ohacoo use more effective in removing ~ .~ idine and anmaonia than the filter tip. "~ .~i~,~. .. . ~kn~ factors affect the amount of nicotine found in the smoke, a. increase D .... .~'.i in the rate of stuck/rig, the volume and duration of puff, in ~o~cco weight (tightness ~ " ~of pack) or a decrease in moisture content of the tobacco leads to a significant .< ~ '~., increase in the percentage of nicotine. The ~}~e of cigarette paper used appears ~ ~ o. be of little consequence. ~ ~ ~'~ ~ Alkaline smoke contains a greater percentage of the tobacco nicotine than • ~'~~ ~.:.. : "-. ~ • • '~'-'~ : .... " : nt :~,:.~, acidic sm~,ke. In tohacoos of the acid type there appears to ~" ee ni~'0tine in s t f0~ and thus delay its volatilization sufficiently so ~ .~.~ ~ that thor ~urned or goes off in the "side stream . Dittman has decreased ~" i ~:~' ....... ~ • . the umoumt~of Dicotine, pyridine bases, ammonia, an~ tars in sacks by treating

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER ~ust be due to the presence of i~ritants other than nicotine. ~ree r,~cotine is lowest in Oriental hranSs, ~hicb are reporte~ to be less Arrltatin=~. Bogen fuz-ther states that irritation frc~ f:'ee nicotine ap~.~ears to be ~uo en~irsly to the caustic ~ effect of its alkalinity since the neutral salts of nicotine show no irritatin~ , effects. ~ The average A~arican cigarette contain~ from about 1.8 to tins on the basis of ~ry ~ei~ht. The amount passir~ into the "=-in strosm" smoke ' 'i~:'~" has been reported as ran~ir~ from about i0 to 93 percent, depon~ir~ on mazmor of ...... ' snok~. Larson and .~aaE report a 22% transfer when t~o-thir~s of the cigarette is' consumed. Thirty-seven percent of the nicotine in the burned portion is co~,pletely destroyed at the burning end, about 35 to 38 percent goes off into the atr~osph~ro An the "side stream" smoke and shout 3 to 6 percent con~,nses and collects in ~h~ ~tte ~arson repol'ts 3 inC. of nicotine, in the smoke of one cicarette while ~'a~ford end his associates report So66 mC...'.er !item- of smoke. The amount of nico~ins absorbed by' the smoker ~e:~en~ on duration and e~ent of ~ontsct of smoke with the mucous mem~ranss of the oral and respiratory passages.

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER According to Larson ordinnry s~okinc without.~inhelati°n lea~s to absorption of about five percent of nicoti~ contained in %~ i~plr~d sm~O (a~u% 0.i~ ~. ~ ~r cigarette) while up to ~ (about 2.7 ~. ~er cigarette) can ~ absorbed on Sno~ ~h i~istion. Wh~e et~l alcohol ~s been reported in trace amo~ts in smoke, met~l ~ ~t~l alcohol in to~cco ~ the fo~ of a ~t~l ester ~ ~ct~c a~d a~ as a other c~po~ ~ ~g~n. ~eberg a~ ~e~teln reported ~t one-tenth of the o~g~ net~l alcohol ~ smoke leaves the mouth ~h the ~eath, the reminder ~ ~issolved ~ saliva. The smoker cons~ng ten average sized cigars absor~ ~ ~. of mot~l alcohol a day. Co,option of 20 cigarettes moa~ abso~tion of ~ ~. of methyl alcohol. Wenusch indicates t~t methanol constitutes a 5-~ of the , so~d-~q~d portion of sm~e fr~ acidic to~cc~, while ov~ i% of tile soli~-liq~d ~rtion of smoke fr~ alkaline The prese~e of alde~des, phenols, ~d dec~position pr~ucts of s~ ca~es the ~in stre~ s~ke to have a power~ reduci~ action. These reduci~ subs~nces ~e pro~ fo~ed ~ the ~o~sis of cell~os~, pect~, starch, and ~g~n. They also ~ve ~en reported to orlg~te fro= the ~cid~, r~s~ and re~n acids. ;.~rl i~icated a co~ection bet~en alde~des and ketches and aro~ of to~cco and ~lieves to~cco resi~ to ~ a s~ce of alde~+os a~ ;~etones, to which he attributes the aromatic neture of the smoke from tobaccos bach in resin content. The aldehydes and ketches have been reported in smoke, to the e~tent of 7 ng,~ per gram of tobacco and as 2.00 rag. per cigarette. FormaldeI~v~e, acetaldehyde, but~aldehydo, diethylkctonc, and dipropyl ketone have been identified. ~enusch

Ol&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER acid l~'drolysls. It woul~ seem tl~t ti:ere is little ~oeeibility that sugars generally could be present in smoke. The correlation ~et~een resin content ar~ quali~y has bean very ~r~ inve~%Igstlo~ (Xopsri~ and I,~li~ri) 1~ioete~ a ~h rea~ ~o~eeo as more desirable. ~ever, content ~s ~es~a~e sl~e resA~ reset causi~ a ~uch ~her parentage ~ ~cot~ u~sopon.lfieble an~ more volatile oils than p~orer grades. • r Phenols imve ol~ays ~en considered a ais~ificant factor ~n the flavo~ ~f s~oke end are a d£stln~u~s)~i~g characteristic of one or ~ore of ~% o~ ia there a c~raoterlsti~ t~e o£ flav~ assoclate~ ~th ~enols ~t they a~peer, In a sere, ~o n~b the to~e to other factors. ~k~ to.coo As ~h in ~henol content which Is d~oct~ ~ra~er~ to

the smoke strenm. In sddltion, it |ms heon pro'posed tba% phenols are formed by pyrolysis and degradation o£ the cel/ulo~e in to[~cco. %~en~ch ~'oported cigarette snoke as contalninc 0.50 phenols. ~3yburn |ms isolated phenol, Cu~lacol, and ortho-cresol in the snoke of fou/ di£ferent typos of cb:~r.~.ttes. The follo~Ir~ results of his determinations are expressed in milli~jrams per liter o£ smoke: Tobacco ?y~e R~enol Guaiacol ].~ts-Cresol Ortho-Cres el ~ri~ht .508 .073 .073 .085 Bu~ley .3?0 .~5~ .O61 .O81 Turkish .337 .044 .049 .069 ~.~rylan~ .420 .065 .068 .085 I~rson and }hag report 0.4 ~illi~ra~ns o£ ph~olic resin per cigarette. The tars of tobacco smoke have been defined in our laboratory as those neutral and acidic suUstances soluble in c~loroforu and non-volaSile at 100°C. ~nile the e~act m~turs of tars is not known, variou~ constituents ~mve ~en reported The ethereal oils, hisher ~drocarbo~, resin, and resin acids already present in~ ~', ~e to~cco appear in the tar. The o~y c~racteri~tic tar ~t~rials t~mt }rove been~ ~ isolated are a ~, ~her allp~tic ~drocar~n and ez~eno w~ch ~s reported ~ ~oda. , ~ The to~cco ~ars ~ reason of ~heir amo~s can be ass~ed to play an i~ortant ~r~ in smo~, a~ ~v~ ~en the subject of much controversy recently. Nen~ch ~s ~oposed tl~t the ~cher hydrocarb~ of tars settle o~ ~he ~uco~ ~smbranes of ~he since:or and for= a =ec|~nlcal protection ecainst the afSsct of irrltatin~ smuke ingrcdion~ of the nicotine. Tobacco tar is also the carrier of substances pertainlr~ to ~aste and odor. '~ The anount of tars produced will vary with smokir~ conditions. Larson ar~ +i' 650379 3:Z, • ~ -' - " . - 24 ":' ~ ~" "~"~~' ~ ~'~ ' - " ~' ' ~

~B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER Haag report 40 m~. of .dry solids" (inclu~ir~ tare) per cigarette in the smoke of ' an average ciEarstta collected b7 dra~ing 35 cc. puffs" of two seconds duration~ on~o: a ~Inute until t~o-thirde o£ the cigarette was consigned, studios at ~ro~n endII ~illia~son on non-filter tip cicarsttes indicate the amount to be in the rar~e of 12-18 m~. per cigarette for most popu~ar h~ar~s. lnorsan4c substances in trace amounts have been reported to be present in smoke. As mentioned, they possibly serve a~ nnclei An part4c~e ~mation. Dr. ~o~ha has reported the £o~o~ing concentrations of elements Ja~ s~ks. Element C°ncentration Copper 0.00005% Load 0.0005% Alu~Inum O .0OO5% l-hngnnes e O .0005% Silicon 0.O05% Calci~ 0.005% Sodium 0.003% Potassium 0.023% ~ecticides and other ,~ttar foreign to the tohacco plaut itself may, of course, find their ~ay £nto the smoke, a fact ~hich in some ~asas constitutes a proble~ in to~cco operations. Load arsenate has been very popular in s~ne tobacco growing sections o£ the United States as an insecticide. Investigations have revealed the presence of arsenic in tobacco products and their smoke. ~arksdate An noting the a~sence o£ arsenic in tobacco not treated ~ith an insecticide, concluded that the insecticides ~ere the source of arsenic. Definite conclusions have not been drawn as to whather volatile arsenic in tobacco 8~oke is free or in a ~Cllnbinad fern. Theoretically, it is believed that arsenic is volatilized as arsenious oxide to vhlch fern it has been converted by the conditions if incomplete

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER conurbation present during smoking. YJ~ recent years a concerted effort has been •ade to have farmers refrain from using arsenical materials an~ thus eliminate this potontisl health hazard fro~ tobacco products. The amount o£ arsenic volatilized varlss from zero to 40~,, depending on the ori~i~al concentration in tobacco. These a~ounts, ho~evar, are not proportional in that a eli~ht increase in the arsenic content of tobacco ca-~ses the areer~tc already prese~nt to be even more volatile. C~rbon monoxide ghlch is a constituent of the gaseous phase of the deserves serious co~sideration in viev of its biological ~JzplicatAona. ~t ¢s sald to be present to the extent of i to 4 volune percent of the total gases. Lateen and P~ag report 15 cc./ci~arette, ~ile Tsunara reports 13.4 to 3V.6/ci~arette, Bogen has found the carbon mono.'~ide concentration increases rapidly vith faster snoking. I expect that there can be little doubt that this phenomena is related to the completeness of the combustion, although the specific ~echanism ~ight be a reduction of carbon dioxide in or near the center of the combustion area. According to Wenusch h~drogen sulfide is 0.04 to 0.007% t~ vol~e o£ the gaseous portion. Fishel a~d ~askine found 0.012 m~. per cigarette or 0.001~% ~ volt, he of s~oke, l~drocyanic acid has been reported as 0.27 to 0.036 cc. pe~ gram tohacco and .020-.034% by vol~ne, end 0.06 rag. per cigarette. Snoko from the acidic type toheccos contain b~vdrocyanic acid in the gaseous portion, vhile from ~a~,kaline tobaccos it is foun~ An the solid-liquid portion. Rapi~ smoking increases the a~aounts of both hydrogen sulfide and hydrocyanic acid. Thlocyanic acid, along ~ith l~drogen sulfide, has been found ~n both the gaseou~ land solid-liquid phase. ,~ Scholler and ~enuseh agree in regarding the sulfur content of the tobacco proteins as the source of those t~o gases. ~t appears that dauger t~ the smoker is ne~*ligible fr¢~ the ~28~ ~D~, and ~CM ~hlch is in cigarette s~oke.

CONFIDENTIAL MINNESOTA TOB~,CCO:LITIGATION

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(15) (C~TO~.~ co B~.~t~r 8~tla.e to aloof*,,,,, Jo d~ta |e ~a~a llo~ ~entl~e~ ]Io~ aantlm~d ]~ ~-ta ~o 8~1~r ~o nXeot/~ne t~, CONFIDENTIAL MINNF~qOTA TOBACCOI L_!TI.GA_TION .....

CONI,11)EN'IIAI, MINNESOTA TOBACCO LITIGATION :~ "

c0~F~NTIAL MINNESOTA TOBACCO L|T|GATION::: " 10)

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CONFIDENTIAL MINNESOTATOBACCOLIT1GATION (~0) /,~ .

• (B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER

(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER (22)

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(B&W) PROTECTED BY MINNESOTA TOBACCO LITIGATION PROTECTIVE ORDER

' S c ~ (B&W) PROTECTED ]BY MIN ESOTA TOBA CO LITIGATION PROTECTIVE ORDER April 1954

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