U.S. patent application number 12/120121 was filed with the patent office on 2008-10-02 for method of making a smoking composition.
This patent application is currently assigned to Liggett Vector Brands Inc.. Invention is credited to Robert D. Bereman.
Application Number | 20080236602 12/120121 |
Document ID | / |
Family ID | 26938497 |
Filed Date | 2008-10-02 |
United States Patent
Application |
20080236602 |
Kind Code |
A1 |
Bereman; Robert D. |
October 2, 2008 |
METHOD OF MAKING A SMOKING COMPOSITION
Abstract
The present invention relates to smoking articles such as
cigarettes, and in particular to catalytic systems containing
metallic or carbonaceous particles that reduce the content of
certain harmful or carcinogenic substances, including polyaromatic
hydrocarbons, tobacco-specific nitrosamines, carbazole, phenol, and
catechol, in mainstream cigarette smoke and in side stream
cigarette smoke.
Inventors: |
Bereman; Robert D.; (Apex,
NC) |
Correspondence
Address: |
KNOBBE MARTENS OLSON & BEAR LLP
2040 MAIN STREET, FOURTEENTH FLOOR
IRVINE
CA
92614
US
|
Assignee: |
Liggett Vector Brands Inc.
Morrisville
NC
|
Family ID: |
26938497 |
Appl. No.: |
12/120121 |
Filed: |
May 13, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11253430 |
Oct 19, 2005 |
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12120121 |
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10871863 |
Jun 18, 2004 |
6959712 |
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11253430 |
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10007724 |
Nov 9, 2001 |
6789548 |
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10871863 |
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60247163 |
Nov 10, 2000 |
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60322132 |
Sep 11, 2001 |
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Current U.S.
Class: |
131/361 |
Current CPC
Class: |
A24B 15/288 20130101;
A24B 15/246 20130101; A24B 15/28 20130101; A24B 15/245 20130101;
A24B 15/287 20130101; A24D 3/163 20130101 |
Class at
Publication: |
131/361 |
International
Class: |
A24D 1/18 20060101
A24D001/18 |
Claims
1. A smoking article comprising a tobacco cut filler with catalytic
metal oxide particles disposed thereon, wherein the metal oxide
particles have an average particle size of less than 500 nm, the
smoking article further comprising at least one nitrate or nitrite
source selected from the group consisting of alkali metal nitrate,
alkaline earth metal nitrate, alkali metal nitrite, alkaline earth
metal nitrite, zinc nitrate, zinc nitrite, and mixtures thereof,
wherein the concentration of nitrogen in the tobacco cut filler
from the nitrate or nitrite source is from about 0.4 to about 1.5
wt. % nitrogen.
2. The smoking article of claim 1, wherein the metal oxide
particles have an average particle size of less than 50 nm.
3. The smoking article of claim 1, wherein the metal oxide
particles have an average particle size of less than 5 nm.
4. The smoking article of claim 1, wherein the metal oxide
comprises a transition metal.
5. The smoking article of claim 1, wherein the metal oxide
comprises at least one metal selected from the group consisting of
palladium, platinum, rhodium gold, cobalt, and copper.
6. The smoking article of claim 1, wherein the metal oxide is
selected from the group consisting of iron oxide, silver oxide, and
zinc oxide.
7. The smoking article of claim 1, comprising an agglomeration or
cluster of two or more metal oxide particles.
8. The smoking article of claim 1, comprising a support material,
wherein metal oxide particles are disposed on the support
material.
9. The smoking article of claim 8, wherein the support material
comprises silica or alumina.
10. The smoking article of claim 1, wherein the metal oxide
particles are crystalline.
11. The smoking article of claim 1, wherein a concentration of
catalytic metal oxide particles in the tobacco cut filler is from
0.005% (w/w) to 0.15% (w/w).
12. The smoking article of claim 1, wherein the tobacco cut filler
further comprises a reducing agent.
13. The smoking article of claim 12, wherein the reducing agent is
a reducing sugar.
14. The smoking article of claim 12, wherein the reducing sugar is
sorbitol.
15. The smoking article of claim 12, wherein the reducing agent is
a polyhydric alcohol.
16. The smoking article of claim 15, wherein the polyhydric alcohol
is selected from the group consisting of glycerol, ethylene glycol,
and propylene glycol, and polyglycol.
17. The smoking article of claim 1, wherein the alkaline earth
metal is calcium.
18. The smoking article of claim 1, wherein the alkaline earth
metal is magnesium.
19. The smoking article of claim 1, wherein the alkaline earth
metal nitrate is magnesium nitrate.
20. The smoking article of claim 1, wherein the alkaline earth
metal nitrate is Mg(NO.sub.3).sub.2-6H.sub.2O.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser.
No. 11/253,430 filed Oct. 19, 2005, which is a continuation of U.S.
application Ser. No. 10/871,863 filed Jun. 18, 2004, now U.S. Pat.
No. 6,959,712, which is a continuation of U.S. application Ser. No.
10/007,724 filed Nov. 9, 2001, now U.S. Pat. No. 6,789,548, which
claims the benefit of U.S. Provisional Application No. 60/247,163
filed on Nov. 10, 2000 and U.S. Provisional Application No.
60/322,132 filed Sep. 11, 2001.
FIELD OF THE INVENTION
[0002] The present invention relates to smoking articles such as
cigarettes, and in particular to catalytic systems containing
metallic or carbonaceous particles that reduce the content of
certain harmful or carcinogenic substances, including polyaromatic
hydrocarbons, tobacco-specific nitrosamines, carbazole, phenol, and
catechol, in both mainstream cigarette smoke and side stream
cigarette smoke.
BACKGROUND OF THE INVENTION
[0003] It is widely known that tobacco smoke contains mutagenic and
carcinogenic compounds that cause substantial morbidity and
mortality to smokers. Such compounds include polyaromatic
hydrocarbons (PAHs), tobacco-specific nitrosamines (TSNAs),
carbazole, phenol, and catechol.
[0004] The carcinogenic potential of polyaromatic hydrocarbons
(PAHs) is well known. PAHs are a group of chemicals where
constituent atoms of carbon and hydrogen are linked by chemical
bonds in such a way as to form two or more rings, or "cyclic"
arrangements. For this reason, these are sometimes called
polycyclic hydrocarbons or polynuclear aromatics. Examples of such
chemical arrangements are anthracene (3 rings), pyrene (4 rings),
benzo(a)pyrene (5 rings), and similar polycyclic compounds.
[0005] Such compounds have been identified in all situations where
combustion of organic materials is taking place, and where
pyrolysis is incomplete. Several industrial sources of these
compounds are known: incomplete pyrolysis of coke in metallurgy, in
aluminum pot rooms, and of fuel oil in heat generating equipment,
to name but a few. It is also known that internal combustion
engines (diesel or gasoline engines) are a major source of these
pollutants. Incomplete combustion of the most simple hydrocarbon,
methane, often referred to as natural gas, has also been found to
be a source of 3,4-benzopyrene emissions. PAHs have also been
identified in tobacco smoke. Several of these PAHs are known to be
carcinogens for lung tissue and others are suspected of similar
effects, operating by genotoxic mechanisms, and their presence in
tobacco smoke has further been linked with the synergism observed
in smokers exposed to high levels of respirable dusts in
uncontrolled workplace situations.
[0006] Tobacco specific nitrosamines (TSNAs) are electrophilic
alkylating agents that are potent carcinogens. They are formed by
reactions involving free nitrate during processing and storage of
tobacco, and by combustion of tobacco containing nicotine and
nornicotine in a nitrate rich environment. It is also known that
fresh-cut, green tobacco contains virtually no tobacco specific
nitrosamines. See, for example, U.S. Pat. No. 6,202,649 and U.S.
Pat. No. 6,135,121 to Williams; and Wiernik et al., "Effect of
Air-Curing on the Chemical Composition of Tobacco," Recent Advances
in Tobacco Science, Vol. 21, pp. 39 et seq., Symposium Proceedings
49th Meeting Tobacco Chemists' Research Conference, Sep. 24-27,
1995, Lexington, Ky. In contrast, cured tobacco products obtained
according to conventional methods are known to contain a number of
nitrosamines, including the two most harmful carcinogens
N'-nitrosonornicotine (NNN) and
4-(N-nitrosomethylamino)-1-(3-pyridyl)-1-butanone (NNK). Of these
two, NNK is significantly more dangerous than NNN. It is widely
accepted that such nitrosamines are formed post-harvest, during the
conventional curing process, and in the combustion process.
[0007] Carbazole, phenol, and catechol are all compounds produced
in cigarette smoke. Carbazole is a heterocyclic aromatic compound
containing a dibenzopyrrole system and is a suspected carcinogen.
The phenolic compounds in cigarette smoke are due to the pyrolysis
of the polyphenols chlorogenic acid and rutin, two major components
in flue-cured leaf Currently, the literature identifies catechol,
phenol, hydroquinone, resorcinol, o-cresol, m-cresol, and p-cresol
as the seven phenolic compounds in tobacco smoke. Catechol is the
most abundant phenol in tobacco smoke (80-400 .mu.g/cigarette) and
has been identified as a co-carcinogen with benzo[a]pyrene (also
found in tobacco smoke). Phenol has been shown to be toxic and is
identified as a tumor promoter in the literature.
[0008] The most common method for removing harmful components from
tobacco smoke is the use of a mechanical filter device. Various
filters for reducing or removing undesirable components from
tobacco have been proposed and constructed. In general, a porous
filter may be provided as a mechanical trap for harmful components,
interposed between the smoke stream and the mouth. This type of
filter, often composed of cellulose acetate, mechanically or
adsorptively traps a certain fraction of the components present in
smoke.
[0009] Cigarette filter devices may contain a variety of granular
or particulate adsorbents in addition to any porous materials,
e.g., cellulose acetate tow, present in the device. Activated
carbon, or charcoal, is the most widely preferred granular
adsorbent. Other types of adsorbents include, for example, kaolin
clay as disclosed in U.S. Pat. No. 4,729,389. U.S. Pat. No.
3,650,279 discloses a cigarette filter composed of a powdered
aluminum silicate mineral that may be prepared by rendering the
mineral electropositive and then cationizing it by absorbing
macromolecular cations (such as methylene blue and FeSO.sub.4)
thereon. U.S. Pat. No. 3,428,054 discloses a cigarette filter
composed of mineral particles, such as slag, and absorptive
powdered clay, such as kaolinite, bound together by a non-toxic
binder. U.S. Pat. No. 3,251,365 discloses a cigarette filter
composed of powdered clay, such as kaolin, into which from 1 to 13
percent by weight of iron or zinc oxide may be incorporated. U.S.
Pat. No. 2,967,118 relates to a specially prepared kaolin clay
powder which has been acid activated for use in filters. U.S. Pat.
No. 4,022,223 teaches the use of alumina and activated alumina as
base materials in absorptive filter compositions.
[0010] An improvement in the effectiveness afforded by
mechanical-type filters or filters containing adsorptive materials
may be provided by including means for chemically trapping or
reacting undesirable components present in smoke. For example, U.S.
Pat. No. 5,076,294 provides a filter element containing an organic
acid, such as citric acid, which reduces the harshness of the
smoke. Inclusion of L-ascorbic acid in a filter material to remove
aldehydes is disclosed in U.S. Pat. No. 4,753,250. U.S. Pat. No.
5,060,672 also describes a filter for specifically removing
aldehydes, such as formaldehyde, from tobacco smoke by providing a
combination of an enediol compound, such as dihydroxyfumaric acid
or L-ascorbic acid, together with a radical scavenger of aldehydes,
such as oxidized glutathione or urea, or a compound of high
nucleophilic activity, such as lysine, cysteine,
5,5-dimethyl-1,3-cyclohexanedione, or thioglycolic acid. U.S. Pat.
No. 5,465,739, the contents of which is incorporated herein by
reference in its entirety, discloses cigarettes incorporating a
filter element containing an acidic material having a pKa at
25.degree. C. of less than about 3, such as phosphoric acid. U.S.
Pat. No. 5,409,021 discloses a double or triple chamber cigarette
filter containing lignin, which is effective in reducing levels of
tobacco-specific nitrosamines.
[0011] While the filters present on most available cigarettes are
effective in reducing levels of certain undesirable components in
tobacco smoke, filters still allow a significant amount of
undesirable compounds to pass into the mouth. Moreover, while
filters may be preferred to reduce the amount of undesired
components in mainstream smoke, which is the smoke that is drawn
through the mouth end of a smokable article or device and inhaled
by the smoker, filters do not reduce the amount of undesirable
components in sidestream smoke. Sidestream smoke is the smoke that
is given off from the end of a burning tobacco product between
puffs and is not directly inhaled by the smoker. Sidestream smoke
gives rise to passive inhalation on the part of bystanders, and is
also referred to as second-hand smoke.
[0012] One approach to removing undesired components from tobacco
smoke is the use of catalysts. Palladium catalyst systems have been
proposed for cigarettes. The following patents describe such
systems: U.S. Pat. No. 4,257,430 to Collins et al.; U.S. Pat. No.
4,248,251 to Bryant et al.; U.S. Pat. No. 4,235,251 to Bryant et
al.; U.S. Pat. No. 4,216,784 to Norman et al.; U.S. Pat. No.
4,177,822 to Bryant et al.; and U.S. Pat. No. 4,055,191 to Norman
et al., each of which is incorporated by reference in its entirety.
Early attempts at incorporating catalytic systems into
mass-produced cigarettes have met with limited success. Therefore,
a catalytic system that reduces the levels of certain carcinogenic
or otherwise undesirable components from tobacco smoke, and which
is amenable to use in mass-produced cigarettes, is desirable.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 provides a typical catalyst chromatogram providing
palladium particle diameters (.mu.m) in a typical reducing solution
after reaction.
[0014] FIG. 2 shows the percent conversion of palladium ion to
palladium in an aqueous solution of low invert sugar over a 5 hour
reaction at 70.degree. C. with samples analyzed every hour.
[0015] FIG. 3 provides PAH levels for various experimetal charcoals
in a cavity filter.
[0016] FIG. 4 provides a HPLC spectrum of nitroPAH standards, from
left to right: 1,6-diaminopyrene, 1,8-diaminopyrene, 4-aminopyrene,
1-aminopyrene and 6-aminochrysene.
[0017] FIG. 5 is a typical HPLC chromatogram for PAH analysis, from
left to right: hydroquinone, resourcinol, catechol, phenol, and
o-cresol.
[0018] FIG. 6 illustrates the increase in volatile level on a per
puff basis as measured using a residual gas analyzer.
[0019] FIG. 7 illustrates the gas phase removal efficiency of
CAVIFLEX filters containing different weights of active carbon 208C
mixed with semolina.
[0020] FIG. 8 provides gas phase retention for dual coal filters
containing 20, 40, 60, 80, and 100 mg carbon, respectively.
[0021] FIG. 9 illustrates the gas phase removal efficiency of the
different versions of the CAVIFLEX filters containing active carbon
BR255 mixed with inert carbon compared to traditional charcoal
filters.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Introduction
[0022] The following description and examples illustrate the
preferred embodiments of the present invention. Those of skill in
the art will recognize that there are numerous variations and
modifications of this invention that are encompassed by its scope.
Accordingly, the description of preferred embodiments should not be
deemed to limit the scope of the present invention.
[0023] While various methods have been provided for removing PAHs,
TSNAs, phenolic compounds, and other undesirable components from
automotive and industrial exhaust gases, no satisfactory method has
been proposed for selectively removing such components from smoke
from a smokable material, for example, tobacco in a cigarette or
cigar, or pipe tobacco. There is, therefore, a need for an improved
smokable material that has reduced levels of certain PAHs, TSNAs,
phenolic compounds, and certain other undesirable components in
both its mainstream and sidestream smoke. Further, there is a need
for a method of substantially reducing certain PAHs, TSNAs,
phenolic compounds, and other undesired components in tobacco smoke
while retaining satisfactory flavor. Moreover, there is a need for
a method of reducing the level of exposure to carcinogenic and
other undesirable components of a smoker or an individual exposed
to sidestream smoke. Such improved smokable materials are
preferably simple to manufacture and convenient to use.
[0024] The preferred embodiments relate to smoking articles such as
cigarettes, cigars, or pipe tobacco, and in particular to
cigarettes having reduced content of various PAHs, the TSNA
4-(N-nitrosomethylamino)-1-(3-pyridyl)-1-butanone (NNK), phenolic
compounds including catechol and phenol, carbazole, and certain
other undesired components in cigarette smoke, including both
mainstream and sidestream smoke. The tobacco products of preferred
smoking articles include a catalytic system including metallic or
carbonaceous particles and a source of nitrate or nitrite. While
not wishing to be limited to any particular mechanism, it is
believed that the nitrate or nitrite source forms nitric oxide
radicals during combustion of the smokable material, and it is
believed that the metallic or carbonaceous particles catalyze the
conversion of nitrate or nitrite to nitric oxide radical. The
nitric oxide radicals are believed to act as a trap for other
radicals that are responsible for formation of PAHs and other
carcinogenic compounds.
[0025] While the compositions and methods of preferred embodiments
generally refer to tobacco, particularly in the form of cigarettes,
it is to be understood that such compositions and methods encompass
any smokable material or smokable composition, as will be apparent
to one skilled in the art.
The Catalyst System
[0026] In preferred embodiments, a catalyst system including
catalytic metallic and/or carbonaceous particles and a nitrate or
nitrite source is incorporated into the smokable material so as to
reduce the concentration of certain undesirable components in the
resulting smoke. In embodiments wherein the particles are metallic,
the particles are preferably prepared by heating an aqueous
solution of a metal ion source and a reducing agent, preferably a
reducing sugar or a metal ion source with hydroxide. Preferably,
after the metallic particles are formed in solution, the nitrate or
nitrite source is added to the solution, and the solution is
applied to the smokable material. However, embodiments in which the
particles and the nitrate or nitrite source are added separately to
the smokable material are also contemplated.
[0027] Metallic Particles
[0028] In preferred embodiments, particles of a catalytic metallic
substance are applied to the smokable materials. The term
"metallic", as used herein, is a broad term and is used in its
ordinary sense, including without limitations, pure metals,
mixtures of two or more metals, mixtures of metals and non-metals,
metal oxides, metal alloys, mixtures or combinations of any of the
aforementioned materials, and other substances containing at least
one metal. Suitable catalytic metals include the transition metals,
metals in the main group, and their oxides. Many metals are
effective in this process, but preferred metals include, for
example, Pd, Pt, Rh, Ag, Au, Ni, Co, and Cu.
[0029] Many transition and main group metal oxides are effective,
but preferred metal oxides include, for example, AgO, ZnO, and
Fe.sub.2O.sub.3. Zinc oxide and iron oxide are particularly
preferred based on physical characteristics, cost, and carcinogenic
behavior of the oxide. A single metal or metal oxide may be
preferred, or a combination of two or more metals or metal oxides
may be preferred. The combination may include a mixture of
particles each having different metal or metal oxide compositions.
Alternatively, the particles themselves may contain more than one
metal or metal oxide. Suitable particles may include alloys of two
or more different kinds of metals, or mixtures or alloys of metals
and nonmetals. Suitable particles may also include particles having
a metal core with a layer of the corresponding metal oxide making
up the surface of the particle. The metallic particles may also
include metal or metal oxide particles on a suitable support
material, for example, a silica or alumina support. Alternatively,
the metallic particles may include particles including a core of
support material substantially encompassed by a layer of
catalytically active metal or metal oxide. In addition to the
above-mentioned configurations, the metallic particles may in any
other suitable form, provided that the metallic particles have the
preferred average particle size.
[0030] The particles may be prepared by any suitable method as is
known in the art. When preparing metallic particles, suitable
methods include, but are not limited to, wire electrical explosion,
high energy ball milling, plasma methods, evaporation and
condensation methods, and the like. However, in preferred
embodiments, the particles are prepared via reduction of metal ions
in aqueous solution, as described below.
[0031] While any suitable metal, metal oxide, or carbonaceous
particle (as described below) is preferred, it is particularly
preferred to use a metal, metal oxide, or carbonaceous particle
that has a relatively low level of transfer to cigarette or other
smoke condensate produced upon combustion of the smokable material.
For example, palladium has a lower level of transfer than silver.
Also, metal oxides tend to have relatively low levels of transfer.
However, in certain embodiments it may be preferred to use a metal,
metal oxide, or carbonaceous particle having a relatively high
level of transfer to smoke condensate. In providing a compound that
effectively catalyzes the decomposition of nitrate salts, it is
also generally preferred that the metal, metal oxide, or
carbonaceous particle have a relatively low specific heat.
Carbonaceous Particles
[0032] In certain embodiments, particles of a catalytic
carbonaceous substance are applied to the smokable materials. The
term "carbonaceous", as used herein, is a broad term and is used in
its ordinary sense, including without limitations, graphitic
carbon, fullerenes, doped fullerenes, carbon nanotubes, doped
carbon nanotubes, other suitable carbon-containing substances, and
mixtures or combinations of any of the aforementioned
substances.
[0033] The carbonaceous particles may be prepared by any suitable
method as is known in the art. When preparing graphitic particles
suitable methods may include, but are not limited to, milling
techniques, and the like.
[0034] Fullerenes include, but are not limited to, buckminster
fullerene (C.sub.60), as well as C.sub.70 and higher fullerenes.
The structure of fullerenes and carbon nanotubes may permit them to
be doped with other atoms, for example, metals such as the alkali
metals, including potassium, rubidium and cesium. These other atoms
may be included within the carbon cage or carbon nanotube, as is
observed for certain atoms when enclosed within endohedral
fullerene. Atoms may also be incorporated into a crystal structure,
e.g., the bct structure of A4C60 (wherein A=K,Rb,Cs, and
C=buckminster fullerene) or the bcc structure of A6C60 (wherein
A=K,Rb,Cs, and C=buckminster fullerene). Fullerenes may also be
dimerized or polymerized. Certain fullerenes, such as C.sub.70
fullerenes, are known radical traps and as such may be suitable for
use in a catalyst system without the presence of nitrate or other
radical trap generators.
[0035] Fullerenes are preferably prepared by condensing gaseous
carbon in an inert gas. The gaseous carbon is obtained, for
example, by directing an intense pulse of laser at a graphite
surface. The released carbon atoms are mixed with a stream of
helium gas, where they combine to form clusters of carbon atoms.
The gas containing clusters is then led into a vacuum chamber where
it expands and is cooled to a few degrees above absolute zero. The
clusters are then extracted. Other suitable methods for preparing
fullerenes as are known in the art may also be used.
[0036] Carbon nanotubes may be prepared by electric arc discharge
between two graphite electrodes. In the electric arc discharge
method, material evaporates from one electrode and deposits on the
other in the form of nanoparticles and nanotubes. Purification is
achieved by competitive oxidation in either the gas or liquid
phase. Carbon nanotubes may also be catalytically grown. In
catalytic methods, filaments containing carbon nanotubes are grown
on metal surfaces exposed to hydrocarbon gas at temperatures
typically between 500-1100.degree. C. Other techniques for forming
carbon nanotubes include laser evaporation techniques, similar to
those used to form fullerenes. However, any suitable method for
forming carbon nanotubes may be used.
Particle Size
[0037] The particles of preferred embodiments preferably have an
average particle size of greater than about 0.5 micron (0.5 .mu.m),
more preferably greater than about 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2,
1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2 .mu.m. The preferred size
may depend on the metallic or carbonaceous substance. Particle
sizes can be as large as 150 .mu.m or more, more preferably 150,
140, 130, 120, 110, 100, 90, 80, 70, 60, 50, 40, 30, 20, 19, 18,
17, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3 .mu.m or less in
diameter. In other embodiments, preferred particle size may be less
than about 0.5 .mu.m (500 nm), or 400, 300, 200, 100, 90, 80, 70,
60, 50, 40, 30, 20, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 nm or less. In
preferred embodiments, the particles are of a substantially uniform
size distribution, that is, a majority of the metallic particles
present have a diameter generally within about .+-.50% or less of
the average diameter, preferably within about .+-.45%, 40%, 35%,
30% or less of the average diameter, more preferably within .+-.25%
or less of the average diameter, and most preferably within .+-.20%
or less of the average diameter. The term "average" includes both
the mean and the mode.
[0038] While a uniform size distribution may be generally
preferred, individual particles having diameters above or below the
preferred range may be present, and may even constitute the
majority of the particles present, provided that a substantial
amount of particles having diameters in the preferred range are
present. In other embodiments, it may be desirable that the
particles constitute a mixture of two or more particle size
distributions, for example, a portion of the mixture may include a
distribution on nanometer-sized particles and a portion of the
mixture may include a distribution of micron-sized particles. The
particles of preferred embodiments may have different forms. For
example, a particle may constitute a single, integrated particle
not adhered to or physically or chemically attached to another
particle. Alternatively, a particle may constitute two or more
agglomerated or clustered smaller particles that are held together
by physical or chemical attractions or bonds to form a single
larger particle. The particles may have different atomic level
structures, including but not limited to, for example, crystalline,
amorphous, and combinations thereof. In various embodiments, it may
be desirable to include different combinations of particles having
various properties, including, but not limited to, particle size,
shape or structure, chemical composition, crystallinity, and the
like.
[0039] Nitrate or Nitrite Source
[0040] Any suitable source of nitrate or nitrite may be preferred.
Preferred nitrate or nitrite sources include the nitrate or nitrite
salts of metals selected from Groups Ia, Ib, IIa, IIb, IIIa, IIIb,
IVa, IVb, Va, Vb, and the transition metals of the Periodic Table
of Elements.
[0041] In preferred embodiments, the nitrate or nitrite source
includes a nitrate of lithium, sodium, potassium, rubidium, cesium,
magnesium, calcium, strontium, yttrium, lanthanum, cerium,
neodymium, samarium, europium, gadolinium, terbium, dysprosium,
erbium, scandium, manganese, iron, rhodium, palladium, copper,
zinc, aluminum, gallium, tin, bismuth, hydrates thereof and
mixtures thereof. Preferably, the nitrate salt may be an alkali or
alkaline earth metal nitrate. More preferably, the nitrate or
nitrite source may be selected from the group of calcium,
magnesium, and zinc with magnesium nitrate being the most preferred
salt. In a particularly preferred embodiment,
Mg(NO.sub.3).sub.2-6H.sub.2O may be preferred as a nitrate source.
While nitrate and nitrite salts are generally preferred, any
suitable metal salt or organometallic compound, or other compound
capable of releasing nitric oxide may be preferred.
[0042] While not wishing to be limited to any particular mechanism,
it is believed that the nitrate or nitrite source forms nitric
oxide radicals and that this reaction process is catalyzed by the
metallic or carbonaceous particles in the combustion zone of
tobacco. The nitric oxide radicals are believed to act as a trap
for other organic radicals that are responsible for formation of
PAHs and other carcinogenic compounds.
[0043] The temperature at which a particular nitrate or nitrite
source decomposes to form nitric oxide may vary. Since a
temperature gradient exists across the combustion zone of a tobacco
rod, the choice and concentration of the nitrate or nitrite source
may be selected so as to provide optimum production of nitric oxide
during combustion. Certain nitrates and nitrites alone, especially
those of the Group Ia metals, function as effective combustion
promoters, accelerating the burn rate of the smokable material and
decreasing the total smoke yield, but not necessarily decreasing
the quantity of PAHs within the smoke. The nitric oxide yield of
such nitrates may also be relatively low.
[0044] In certain embodiments, it may be preferred that the metal
ion source and the nitrate or nitrite source constitute the same
compound, for example, palladium(II) nitrate.
[0045] Catalyst Preparation
[0046] In preferred embodiments, metallic particles may be prepared
from an aqueous solution. For example, metal particles may be
prepared from an ion source containing one or more metal ion
sources and one or more reducing sugars. Suitable metal ion sources
include any ionic or organometallic compound that is soluble in
aqueous solution and is capable of yielding metal ions that may be
reduced to particles of a catalytic metal or utilized to form a
metal oxide. In a particularly preferred embodiment, the catalytic
source includes a metal such as palladium, and the palladium ion
source includes water-soluble palladium salts. Illustrative
non-limiting examples of suitable palladium salts include simple
salts such as palladium nitrate, palladium halides such as
palladium di or tetrachloride diammine complexes such as
dichlorodiamminepalladium(II) (Pd(NH.sub.3).sub.2Cl.sub.2), and
palladate salts, especially ammonium salts such as ammonium
tetrachloropalladate(II) and ammonium hexachloropalladate(IV).
[0047] One form of palladium that may be especially preferred is
ammonium tetrachloropalladate(II), (NH.sub.4).sub.2PdCl.sub.4.
Ammonium tetrachloropalladate is generally preferred over ammonium
hexachloropalladate because under typical conditions for preparing
the metallic particles, a higher metal ion to metal conversion may
be observed for ammonium tetrachloropalladate(II).
[0048] In a preferred embodiment, an aqueous solution of reducing
agent is prepared, to which the metal ion source is added. In
preferred embodiments, the reducing agent may be a reducing sugar,
however other suitable reducing agents may be preferred. Although
any compound capable of reducing the metal ion can be employed, as
a practical matter the reducing agent is preferably non-toxic and
preferably does not form toxic byproducts when pyrolyzed during
smoking. In addition, the reducing agent is preferably
water-soluble.
[0049] Preferred reducing agents are the reducing sugars, including
organic aldehydes, including hydroxyl-containing aldehydes such as
the sugars, for example glucose, mannose, galactose, xylose,
ribose, and arabinose. Other sugars containing hemiacetal or keto
groupings may be employed, for example, maltose, sucrose, lactose,
fructose, and sorbose. Pure sugars may be employed, but crude
sugars and syrups such as honey, corn syrup, invert syrup or sugar,
and the like may also be employed. Other reducing agents include
alcohols, preferably polyhydric alcohols, such as glycerol,
sorbitol, glycols, especially ethylene glycol and propylene glycol,
and polyglycols such as polyethylene and polypropylene glycols. In
alternative embodiments, other reducing agents may be preferred
such as carbon monoxide, hydrogen, or ethylene.
[0050] The solution is preferably heated before the metal ion
source is added to the solution, and maintained at an elevated
temperature afterwards so as to reduce the time for conversion of
the metal ions to metallic particles. In a preferred embodiment, a
reducing sugar such as low invert sugar may be preferred as the
reducing agent. In certain embodiments, it may be desirable to have
an excess or deficiency of reducing agent present in solution.
Generally, it is preferred to prepare an aqueous solution
containing from about 5 wt. % to about 20 wt. % of the reducing
sugar, preferably about 6 wt. % to about 16 or 17 wt. %, more
preferably from about 7, 8, 9, 10, or 11 wt. % to about 12, 13, 14,
or 15 wt. %. When the reducing agent is invert sugar, it is
preferred to prepare a 11 wt. % to about 12 wt. % solution. The
amount of reducing agent preferred may vary depending on the type
of reducing agent preferred and the amount of metal ion source to
be added to the solution.
[0051] It may be preferred to prepare the solution in a glass-lined
vessel equipped with a heating jacket. In certain embodiments,
however, it may be preferred to prepare the solution in another
kind of vessel constructed of or lined with another type of
material, for example, plastic, stainless steel, ceramic, and the
like. It is generally preferred to conduct the reaction in a closed
vessel. In certain embodiments, it may be desirable to conduct the
reaction under reduced pressure or elevated pressure, or under an
inert atmosphere, such as nitrogen or argon.
[0052] In preparing the aqueous solution of the reducing sugar, it
is preferred to use deionized ultrafiltered water. While in
preferred embodiments the metallic particles are prepared from
aqueous solution, in other embodiments it may be desirable to use
another suitable solvent system, for example, a polar solvent such
as ethanol, or a mixture of ethanol and water. Additional
components may be present in the solution as well, provided that
they do not substantially adversely impact the catalytic activity
of the metallic particles.
[0053] After adding the reducing sugar to the deionized
ultrafiltered water, the solution is preferably heated with
constant mixing so as to avoid hot spots in the solution. Although
in certain embodiments it may be desirable to prepare the particles
from a room temperature solution, or even a solution cooled below
room temperature, it is generally preferred to heat the solution so
as to speed the reaction between the reducing sugar and the metal
ion source once it is added to the solution. The solution may be
heated to any suitable temperature, but boiling of the solution and
decomposition of the reducing sugar is preferably avoided. In a
preferred embodiment wherein low invert sugar is the reducing
sugar, the solution is typically heated up to about 95.degree. C.
or more, preferably from above room temperature to about 90.degree.
C., more preferably from about 50.degree. C., 55.degree. C.,
60.degree. C., or 65.degree. C. to about 85.degree. C., and most
preferably from about 70.degree. C. or 75.degree. C. to about
80.degree. C.
[0054] The metal ion source is added to the heated aqueous solution
of reducing agent, which is stirred while the metal ions react with
the reducing sugar to produce metallic particles. It is generally
preferred to add sufficient metal ion source so as to produce a
solution containing from less than about 3000 ppm to more than
about 5000 ppm metal. Preferably, sufficient metal ion source is
added to produce a solution containing from about 3250, 3500, or
3750 ppm to about 4250, 4500, 4750 ppm metal, more preferably from
about 3800, 3850, 3900, or 3950 ppm to about 4050, 4100, 4150, or
4200 ppm metal, and most preferably about 4000 ppm metal.
[0055] The reaction time for conversion of metal ion to metal
particles may vary depending upon the reducing agent and metal ion
source preferred, but generally ranges from about 30 minutes or
less to about 24 hours or more, and typically ranges from about 1
or 2 hours up to about 3, 4, or 5 hours. In a preferred embodiment,
wherein ammonium tetrachloropalladate is the metal ion source, a
substantial conversion of palladium ion to palladium metal may be
achieved after 3 hours for a solution heated to a temperature of
about 75.degree. C. Although in certain embodiments a lower
conversion may be acceptable, it is generally desirable to achieve
a conversion of metal ion to metal of at least 50%, preferably at
least 60%, more preferably at least 70%, and most preferably at
least 75, 80, 85% or more.
[0056] The metallic particles produced in this manner generally
have diameters of about 1 .mu.m or less. In certain other
embodiments metallic particles having individual diameters and
average diameters below about 20 nm or above about 1 .mu.m may be
produced. The size of the metallic particles may be conveniently
determined using conventional methods of X-ray diffraction or other
particle size determination methods, for example, laser
scattering.
[0057] After a sufficient conversion of metal ion to metal or metal
oxide is achieved, and the metallic particles are formed, the
nitrate or nitrite source is added to the suspension. Any suitable
compound that yields nitrate or nitrite ion in aqueous solution may
be preferred. Preferably, the nitrate or nitrite source is an
alkali metal or alkaline earth metal nitrate or nitrite. In a
particularly preferred embodiment, the nitrate or nitrite source is
magnesium nitrate, Mg(NO.sub.3).sub.2-6H.sub.2O. It is generally
preferred to add a sufficient amount of nitrate or nitrite source
so as to produce a solution containing from less than about 70 ppm
to more than about 100 ppm nitrogen (in the form of nitrate or
nitrite). Preferably, sufficient nitrate or nitrite source is added
to produce a solution containing from about 75, 80, or 85 ppm to
about 90 or 95 ppm nitrogen, more preferably from about 80 ppm
nitrogen.
[0058] Generally, it is preferred that the suspension of metallic
particles not be excessively concentrated or dilute, so as to
facilitate efficient application of the suspension to the smokable
material.
[0059] While it is generally preferred to prepare a suspension of
particles as described above by reduction of metal ion in solution,
followed by addition of the nitrate or nitrite source, in other
embodiments it may be preferred to use a different method to
prepare the particles. If the metallic or carbonaceous particles
are not prepared in solution, the particles may be mixed with an
appropriate liquid to form a suspension. Because of their high
surface area, it may be difficult to sufficiently wet the surface
of the particles so as to form a uniform suspension. In such cases,
any suitable method may be preferred to facilitate forming the
suspension, including, but not limited to, mechanical methods such
as sonication or heating, or chemical methods such as the use of
small quantities of surfactants, provided the surfactants do not
interfere with the catalytic activity of the particles. Once the
suspension is formed, addition of the nitrate or nitrite source may
proceed as described above.
[0060] While it is generally preferred to apply the metallic or
carbonaceous particles and nitrate or nitrite source to the
smokable material in the form of a suspension, other methods of
applying the particles and nitrate or nitrite source are also
contemplated. For example, if the particles are in dry form, they
may be added to the smokable material as a powder. It may be
advantageous to moisten the smokable material with a suitable
substance, for example, water, prior to application of the powder
in order to provide better adhesion of the particles to the
smokable material.
[0061] When the carbonaceous or metallic particles are added to the
smokable material in powder form, the nitrate or nitrate source in
solid form may also be applied to the smokable material in powder
form, either in a separate step before or after the addition of the
particles, or simultaneously with the particles, for example, in
admixture with the particles. Suitable methods as are well known in
the art may be used to prepare a suitable solid form of nitrate or
nitrate source. In particularly preferred methods, the solid form
of nitrate or nitrite source is prepared by freeze drying or spray
drying methods, both of which may yield extremely small particle
sizes. It is generally preferred that the nitrate or nitrite source
be in the form of particles having an average diameter on the order
of the preferred average diameters for the particles. The nitrate
or nitrite source may also be provided as a solution applied to the
smokable material as a separate step from adding the particle
powder, preferably before adding the particle in dry form to the
smokable material.
[0062] Optimization of the Catalyst System
[0063] There are many aspects to consider when attempting to
optimize the catalyst system, the first of which is the conversion
of the palladium salt to palladium metal in the aqueous reducing
solution. This conversion requires a chemical reduction reaction in
an aqueous solution. Earlier work was directed to the conversion of
the palladium salt to palladium metal in a casing solution. It was
suggested from the patent literature that the reducing agent for
this reaction in the casing solution was fructose--a known reducing
sugar. One origin of fructose in the casing solution is from low
invert sugar. In order to try to repeat this earlier research with
casing solutions and produce a more consistent/controllable
reaction, all of the components in the casing solution were
eliminated that were considered non-essential to the reduction
reaction (e.g. propylene glycol, licorice, cocoa, and the like),
while the components thought to be essential (e.g. water, palladium
salt and low invert sugar) were retained in the same ratios as
found in the casing solution, namely 93 g water to 1 g palladium
salt to 8 g low invert sugar per pound of tobacco, respectively.
Another component that was in the original casing solution but is
considered non-essential to the reduction reaction was
Mg(NO.sub.3).sub.2-6H.sub.2O. This component was present in early
formulations, however nitrate analysis of the tobacco verified that
Mg(NO.sub.3).sub.2-6H.sub.2O decomposes to a certain degree when
mixed in aqueous solutions containing palladium metal. It was also
found through early testing that carcinogen reduction in cigarettes
was not reproducible when the Mg(NO.sub.3).sub.2-6H.sub.2O was
allowed to be in contact with palladium metal for extended periods
of time. Upon removal of the Mg(NO.sub.3).sub.2-6H.sub.2O from the
reacting solution, and instead the addition of it prior to catalyst
application on the tobacco, consistent and reproducible carcinogen
reductions in experimental cigarettes were obtainable.
[0064] One feature of the preferred reduction reaction is the
percent conversion of palladium salt to palladium metal in the
aqueous solution containing low invert sugar as a reducing agent.
At a temperature of approximately 70-75.degree. C., the percent
conversion typically increases steadily with time and after the
first three hours of the reaction more than 60-70% of the salt has
typically been converted to the metal. Most of the palladium salt
is typically converted to metal within the first hour
(approximately 50%). Longer reaction times (for example, above
three hours) generally only increase the percent conversion
modestly. Given the task of balancing maximum conversion with an
acceptable production schedule, three hours is generally preferred
as the minimum time for this reaction to occur before application
of the catalyst solution to the tobacco.
[0065] To increase production rates and lower production costs, it
is desirable to increase the percent conversion of palladium salt
to palladium metal. An immediate benefit of increasing the percent
conversion is the capacity to use less total palladium salt in the
reaction as an increase in percent conversion with less salt could
in fact produce equivalent amounts of palladium metal in the
reaction. This results in lower consumption of the most expensive
reagent in the reaction.
[0066] Several possibilities exist to increase the percent
conversion of this reaction. The reduction reaction is based on an
aldehyde being oxidized and releasing electrons to the Pd II
nucleus, thereby producing metallic palladium.
##STR00001##
[0067] In a particularly preferred catalyst system as described
above, it is believed that the aldehyde source is the reducing
sugar fructose. In theory, any compound containing an aldehyde
functional group can reduce the palladium salt to palladium metal,
however to apply the resulting mixture to tobacco it is preferred
that the reducing agent is non-toxic. As discussed previously in
regard to the particularly preferred catalyst system, low invert
sugar is used as the "reducing agent" for this reaction and it is
believed that the fructose component of low invert sugar is the
active reducing agent. Interestingly, pure fructose when supplied
as a reducing agent for the palladium reduction has been shown not
to be very effective, even when the fructose is in 10 molar excess.
This observation suggests that there is an additional "co-reducing
agent" or possibly a catalyst for the reducing agent contained
within the low invert sugar solution. Due to the complex mixture
associated with low invert sugar it will continue to be a challenge
to discover exactly what the reducing agent or agents are when
utilizing low invert sugar as a reactant. Nevertheless, the
particularly preferred system performs remarkably well given the
fact that the mechanism for palladium reduction is not well
understood in this system.
[0068] Application of Catalyst to Smokable Material
[0069] After the nitrate or nitrite source has been added to the
suspension containing metallic or carbonaceous particles, it is
applied to the smokable material. If the smokable material is
tobacco, it is preferred to apply the suspension to cut filler
prior to addition of the top flavor. If a top flavor is not
applied, then it is preferred to apply the suspension to the cut
filler as a final step, for example, before it is formed into a
tobacco rod. The catalytic particles may be applied before, during
or after application of a casing solution, however in a preferred
embodiment the catalytic particles are applied after application of
the casing solution. Casing solutions are pre-cutting solutions or
sauces added to tobacco and are generally made up of a variety of
ingredients, such as sugars and aromatic substances. Such casing
solutions are generally added to tobacco in relatively large
amounts, for example, one part casing solution to five parts
tobacco.
[0070] The particles and nitrate or nitrite source are preferably
well dispersed throughout the tobacco so as to provide uniform
effectiveness throughout the entire mass of smokable material and
throughout the entire period during which the material is smoked.
In the case of cigarette tobacco wherein a blend of various
tobaccos is preferred, the suspension may be applied to one or more
of the blend constituents, or all of the blend constituents, as
desired. Preferably, the suspension is applied to all of the blend
constituents so as to ensure substantially uniform coverage of the
particles and nitrate or nitrite source.
[0071] For certain types of suspensions of particles, a degradation
in performance may be observed if an excessive period of time is
allowed to elapse before the suspension is applied to the smokable
product. This degradation in performance may be due to various
factors, including loss of particles from the suspension due to
their accumulation on the interior surfaces of the reaction vessel,
or an undesirable increase in particle size over time. When the
suspension includes palladium particles, the suspension is
generally applied to the cut filler within about ten hours after
the desired degree of metal ion conversion is reached and the
nitrate or nitrite source is added to the suspension. The
suspension is preferably applied within about 9, 8, 7, or fewer
hours, more preferably within about 6, 5, or 4 hours, and most
preferably within 3, 2, or 1 hours or less. However, in certain
embodiments, including those utilizing palladium particles, it may
be possible to apply the suspension after a delay of longer than
ten hours while maintaining acceptable catalytic performance.
[0072] It is preferred to apply the suspension to the smokable
material in the form of a fine mist, such as is produced using an
atomizer. In a particularly preferred embodiment, the suspension is
applied to tobacco, preferably cut filler, in a rotating tumbler
equipped with multiple spray heads. Such a method of application
ensures an even coating of the metallic particles on the tobacco
product. The tobacco may be heated during or after application of
the solution so as to facilitate evaporation of excess solvent.
[0073] It is preferred to add a sufficient quantity of the metallic
or carbonaceous particle suspension to the smokable material such
that the smokable material contains from about 500 ppm or less to
about 1500 or more ppm of the metal or carbon in the form of
catalytic particles. Preferably, the smokable material contains
from about 500 ppm to about 1000, 1100, 1200, 1300, or 1400 ppm of
the metal or carbon in the form of catalytic particles, more
preferably 500, 600 or 700 to about 800, 900, or 1000 ppm, and most
preferably about 800 ppm. It is generally preferred that the
smokable material contains from about 0.4 to about 1.5 wt. %
nitrogen (from nitrate or nitrite). Preferably, the smokable
material contains from about 0.5 or 0.6 wt. % to about 1.0, 1.1,
1.2, 1.3, or 1.4 wt. % nitrogen, more preferably from about 0.6,
0.7, or 0.8 wt. % to about 0.9 wt. %, and most preferably about 0.9
wt. % nitrogen. In a preferred embodiment, one kilogram of tobacco
constitutes 800 milligrams of metal or carbon in the form of
catalytic particles, and 9 grams of nitrogen in the form of the
nitrate or nitrite source.
[0074] Once the metallic or carbonaceous particles and nitrate or
nitrite source have been applied, the smokable material may be
further processed and formed into any desired shape or used
loosely, for example, in cigars, cigarettes, or pipe tobacco, in
any suitable manner as is well-known to those skilled in the
art.
The Filter
[0075] In preferred embodiments wherein the smokable material to
which the metallic or carbonaceous particles and nitrate or nitrite
source have been applied is fashioned into a smokable article, a
filter for the smokable article is provided. The filter can be
provided in combination with cigarettes or cigars or other smokable
devices containing divided tobacco or other smokable material.
Preferably, the filter is secured to one end of the smokable
article, positioned such that smoke produced from the smokable
material passes into the filter before entering the smoker.
Alternatively, the filter can be provided by itself, in a form
suitable for attachment to a cigarette, cigar, pipe, or other
smokable device utilizing the smokable material to which metallic
or carbonaceous particles and nitrate or nitrate source have been
applied according to preferred embodiments.
[0076] The filter according to preferred embodiments advantageously
removes at least one undesired component from tobacco smoke or the
smoke of any other smokable material. Undesired components in
tobacco smoke may include permanent gases, organic volatiles,
semivolatiles, and nonvolatiles. Permanent gases (such as carbon
dioxide) make up 80 percent of smoke, and are generally unaffected
by filtration or adsorption materials. The levels of organic
volatiles, semivolatiles, and nonvolatiles may be reduced by
filters of various designs. The filters according to preferred
embodiments may advantageously remove undesired components
including, but not limited to, tar, nicotine, carbon monoxide,
nitrogen oxides, HCN, acrolein, nitrosamines, particulates, oils,
various carcinogenic substances, and the like.
[0077] The filter preferably permits satisfactory or improved smoke
flavor, nicotine content, and draw characteristics. The filter is
preferably designed to be acceptable to the user, being neither
cumbersome nor unattractive. Further, filters according to
preferred embodiments may be made of inexpensive, safe and
effective components, and may preferably be manufactured with
standard cigarette manufacturing machinery.
[0078] The filter may incorporate one or more materials capable of
absorbing, adsorbing, or reacting with at least one undesirable
component of tobacco smoke. Such absorbing, adsorbing, or reacting
materials may be incorporated into the filter using any suitable
method or device. In a preferred embodiment, the absorbing,
adsorbing, or reacting material may be contained within a
smoke-permeable cartridge to be placed within the filter, or
contained within a cavity within the filter. In another embodiment,
the absorbing, adsorbing, or reacting material is deposited on
and/or in the filter material.
[0079] Application methods may include forming a paste of the
absorbing, adsorbing, or reacting material in a suitable liquid,
applying the paste to the filter material, and allowing the liquid
to evaporate. Alternatively, the absorbing, adsorbing, or reacting
material may be mixed with an adhesive substance and applied to the
filter material. All of the filter material may include the
absorbing, adsorbing, or reacting material, or only a portion of
the filter material may include the adsorbing or reacting material.
The portion of the filter material containing the absorbing,
adsorbing, or reacting material is generally referred to as a "a
smoke-altering filter segment."
[0080] The cigarette filters of the preferred embodiments
preferably include activated carbon (commonly referred to as
charcoal) as an adsorbing material. The process by which activated
carbon removes compounds is adsorption, which is a different
process than absorption. Absorption is the process whereby
absorbates are dispersed throughout a porous absorbent, while
adsorption is a surface attraction effect. Both adsorption and
absorption can be physical or chemical effects. The adsorptive
effect associated with activated carbon is mainly a physical
effect. In activated carbon filters, smoke compounds in the organic
volatile and semivolatile phases diffuse through the carbon
particles, move over the surface and then move into the activated
carbon pores compelled by a phenomenon known as Van der Waal's
forces. Although these forces are generally considered weak, at
very short range (one or two molecular diameters), they are strong
enough to attract and effectively hold smoke components.
[0081] Activated carbon may be obtained from a variety of sources,
including, but not limited to, wood, coconut shells, coal, and
peat. Wood generally produces soft and macroporous activated carbon
(pores from 50 to 1,000 nm in diameter). Peat and coal materials
generally produce activated carbon that is predominantly mesoporous
(pores 2 to 50 nanometers in diameter). Activated carbon derived
from coconut shells is generally microporous (pores of less than 2
nm in diameter), has a large surface area, and has a low ash and
base metal content when compared to certain other types of
activated carbon.
[0082] Preferred activated carbons are microporous and have a high
density, which imparts improved structural strength to the
activated carbon so that it can resist excessive particle abrasion
during handling and packaging.
[0083] The filters of preferred embodiments may also contain
various other adsorptive, absorptive, or porous materials in
addition to activated carbon as described above. Examples of such
materials, include, but are not limited to, cellulosic fiber, for
example, cellulose acetate, cotton, wood pulp, and paper; polymeric
materials, for example, polyesters and polyolefins; ion exchange
materials; natural and synthetic minerals such as activated
alumina, silica gel, and magnesium silicate; natural and synthetic
zeolites and molecular sieves (see, for example U.S. Pat. No.
3,703,901 to Norman et al., incorporated herein by reference in its
entirety); natural clays such as meerschaum; diatomaceous earth;
activated charcoal and other materials as will be understood by
those with skill in the art. The adsorptive, absorptive, or porous
material may be any nontoxic material suitable for use in filters
for smokable devices that are compatible with other substances in
the smoking device or smoke to be filtered.
[0084] Typically, the filter element may include as the major
component a porous material, for example, cellulose acetate tow or
cellulosic paper, referred to below as a "filter material." The
adsorptive or absorptive component, often a granular or particulate
substance such as activated carbon, is generally dispersed within
the porous filter material of the filter segment or positioned
within a cartridge or cavity (for example, within a cavity of a
triple filter, as discussed below).
[0085] The filter material may have the form of a non-woven web of
fibers or a tow. Alternatively, the filter material may have a
sheet-like form, particularly when the material is formed from a
mixture of polymeric or natural fibers, such as cotton or wood
pulp. Filter material in web or sheet-like form can be gathered,
folded, crimped, or otherwise formed into a suitable (for example,
cylindrical) configuration using techniques which will be apparent
to one skilled in the art. See, for example, U.S. Pat. No.
4,807,809 to Pryor et al., which is incorporated herein by
reference in its entirety.
[0086] In preferred embodiments, the filter material constitutes
cellulose acetate tow or cellulose paper. Cellulose acetate tow is
the most widely preferred filter material in cigarettes worldwide.
Cellulose paper filter materials generally provide better tar and
nicotine retention than do acetate filters with a comparable
pressure drop, and have the added advantage of superior
biodegradability. Cellulose and cellulose acetate reduce the amount
of chemicals in the semivolatile phase and the nonvolatile phase,
which is composed of solid particulates (commonly referred to as
"tar"). These compounds are reduced in direct proportion to the
amount of cellulose or cellulose acetate in the filter. Increasing
density of the cellulose or cellulose acetate generally means
increasing the pressure drop, which increases the filter retention
and therefore decreases tar delivery. Filters retain generally less
than 10 percent of vapor phase components.
[0087] In certain embodiments, it may be preferred to use a
polymeric material such as cellulose acetate as the filter material
rather than a material such as cellulose paper. Polymeric materials
may be preferred in embodiments wherein superior chemical inertness
or structural integrity during use are desired attributes of the
filter, for example, when certain smoke altering components
reactive to cellulose paper are present in the filter, or when
components reactive to cellulose paper are generated within the
filter. Cellulose acetate tow (such as that available from Celanese
Acetate of Charlotte, N.C.) is the most commonly preferred
polymeric material, however suitable polymeric materials may
include other synthetic addition or condensation polymers, such as
polyamides, polyesters, polypropylene, or polyethylene.
[0088] The polymeric material may be any nontoxic polymer suitable
for use in filters for smokable devices that are compatible with
other substances in the smoking device or smoke to be filtered, and
which possess the desired degree of inertness. The polymeric
material is preferably in fibrous tow form, but may optionally be
in other physical forms, for example, crimped sheet. The polymeric
material may constitute a single polymer or a mixture of different
polymers, for example, two or more of components such as
homopolymers, copolymers, terpolymers, functionalized polymers,
polymers having different molecular weights, polymers constituting
different monomers, polymers constituting two or more of the same
monomers in different proportions, oligomers, and nonpolymeric
components. The polymer may also be subjected to suitable
pre-treatment or post-treatment steps, for example,
functionalization of the polymer, coating with suitable materials,
and the like.
[0089] When polymeric fibers are the filter material, they can make
up all or a portion of the composition of the filter material of
the filter. Alternatively, the filter material can be a mixture or
blend of polymer fibers, or a mixture or blend of polymer fibers
and nonpolymeric fibers, for example, cellulose fibers obtained
from wood pulp, purified cellulose, cotton fibers, or the like. A
mixture of filter materials may be preferred in certain embodiments
where it is desired to reduce materials costs, as polymeric
materials may be more expensive than natural fibers. Any suitable
proportion of polymeric material may be present, from 100% by
weight polymeric material down to 80, 60, 50, 40, 30, 25, 20, 15,
or 10% by weight or less polymeric material.
[0090] As discussed above, in certain embodiments it may be
desirable to coat the filter material with one or more substances
that may react chemically with an undesirable component of the
smoke. Such substances may include natural or synthetic polymers,
or chemicals known in the art to provide for a treated filter
material capable of altering the chemistry of tobacco smoke. One
method for coating the filter material is to prepare a solution or
dispersion of the substance with a suitable solvent. Suitable
solvents may include, for example, water, ethanol, acetone, methyl
ethyl ketone, toluene, or the like.
[0091] The solution or dispersion can be applied to the surface of
the filter material using gravure techniques, spraying techniques,
printing techniques, immersion techniques, injection techniques, or
the like. Most preferably, the filter material is essentially
insoluble in the preferred solvent, and as such does not
substantially affect the general structure of the filter material.
After the solution or dispersion is applied to the surface of the
filter material, the solvent is removed, typically by air-drying at
room temperature or heating, for example, in a convection or
forced-air oven. The amount of solution or dispersion which is
applied to the filter material is typically sufficient to cover the
outer surface of the filter material, but not sufficient to fill
the void spaces between the fibers of filter material.
[0092] Typically, the amount of solution or dispersion applied to
the filter material is sufficient to deposit at least about 5
percent, preferably at least about 8 percent, more preferably at
least about 10 percent, and most preferably at least about 15
percent of the substance, based on the weight of the filter
material prior to treatment.
[0093] When the substance is a polymer, the polymer can be
synthetic polymer or a natural polymer. Synthetic polymers are
derived from the polymerization of monomeric materials (for
example, addition or condensation polymers) or are isolated after
chemically altering the substituent groups of a polymeric material.
Natural polymers are isolated from organisms (for example, plants
such as seaweed), usually by extraction.
[0094] Exemplary synthetic polymers that may be applied to filter
materials include, but are not limited to, carboxymethylcellulose,
hydroxypropylcellulose, cellulose esters such as cellulose acetate,
cellulose butyrate and cellulose acetate propionate (for example,
from Eastman Chemical Corp. of Kingsport, Tenn.), polyethylene
glycols, water dispersible amorphous polyesters with aromatic
dicarboxylic acid functionalities (for example, Eastman AQs from
Eastman Chemical Corp. of Kingsport, Tenn.), ethylene vinyl alcohol
copolymers (for example, from Mica Corp. of Shelton, Conn.),
partially or fully hydrolyzed polyvinyl alcohols (for example, the
Airvols from Air Products and Chemicals of Allentown, Pa.),
ethylene acrylic acid copolymers (for example, Envelons from Rohm
and Haas of Philadelphia, Pa. and Primacors from The Dow Chemical
Co. of Wilmington, Del.), polysaccharides (for example, Keltrol
from CP Kelco of San Diego, Calif.), alginates (for example, from
International Specialty Products of Wayne, N.J.), carrageenans (for
example, Viscarin GP109 and Nutricol GP120F konjac flour from FMC)
and starches (for example, Nadex 772, K-4484 and N-Oil from
National Starch & Chemical Co.).
[0095] Typically, natural or synthetic polymers tend to coat the
surface of the filter material very efficiently, and have a high
viscosity, making high coating levels unnecessary and sometimes
difficult. Typically, certain natural or synthetic polymers can be
applied to the filter material at levels of at least about 0.001
percent, preferably at least about 0.01 percent, more preferably at
least about 0.1 percent, and most preferably at least about 1
percent, based on the weight of the filter material prior to
treatment. Typically, the amount of certain natural or synthetic
polymers applied to the filter material does not exceed about 10
percent, and normally does not exceed about 5 percent, based on the
weight of the filter material prior to treatment.
[0096] The natural or synthetic polymeric material which is applied
to the filter material can vary, depending upon factors such as the
chemical functionality, hydrophilicity or hydrophobicity desired.
If desired, more than one type of natural or synthetic polymer can
be applied to the filter material in a single dispersion or
solution. If desired, the filter material can have at least one
type of natural or synthetic polymer dissolved or dispersed in a
suitable solvent applied thereto and the solvent removed, after
which the resulting coated filter material has at least one other
natural or synthetic polymer applied in similar fashion. If
multiple applications are conducted in this way, it is desirable
that the solvent or solvents do not substantially dissolve any
natural or synthetic polymer already coated onto the filter
material.
[0097] Filters of preferred embodiments may include more than one
segment. One configuration of such filters is the dual filter,
wherein the filter constitutes two different segments, with one
segment adjacent to the mouth and the other segment of the filter
adjacent to the tobacco rod. A common type of dual filter is one
wherein a cellulose acetate segment is situated on the mouth side
of the filter, and a cellulose paper segment is situated on the
side of the filter adjacent to the tobacco rod. Activated charcoal
may be incorporated into the cellulose paper segment of the filter
to assist in removal of undesired components from tobacco
smoke.
[0098] Another filter configuration, referred to as a triple
filter, has three segments, including a segment adjacent to the
mouth, a segment adjacent to the tobacco rod, and a segment
situated between the two other segments. The different segments may
be prepared from different materials, or may be materials having
the same composition but different physical form, for example,
crimped sheet or tow, or may be materials having the same
composition and physical form, but wherein one segment contains an
additional component not present in another segment. A common
triple filter configuration includes two segments selected from one
or both of cellulose acetate and cellulose, one adjacent to the
mouth and one adjacent to the filter, with a segment in between
containing a smoke altering component. Examples of smoke altering
components include activated carbon or other absorbents, or
components imparting flavor to the smoke.
[0099] One variety of triple filter is the cavity filter. The
cavity filter is composed of two segments separated by a cavity
containing one or more smoke altering components. The cavity may
contain an adsorbent material as described above, optionally in
combination with other suitable components such as activated
charcoal.
[0100] Dual and triple filters may be symmetrical (all filter
segments are the same length) or asymmetrical (two or more segments
are of different lengths). Filters may be recessed, with an open
cavity on the mouth side, reinforced by an extra stiff plug wrap
paper.
[0101] When the filter element contains a solid material in a form
other than tow or sheet, it may be incorporated into the filter
element using any suitable method or device, such as those
described above for incorporating an absorbing, adsorbing, or
reacting material into the filter element. Liquids may be
incorporated into the porous filter material by immersing the
filter material in the liquid, spraying the liquid onto the filter
material, or combining the liquid with another component, for
example, a component capable for forming a gel or a solid, then
applying the liquid-containing substance to the porous filter
material using methods well known to those skilled in the art.
[0102] The form of the filter material and the configuration of the
filter material, as well as the filtration efficiency for
particulate matter and vapor phase components of each segment of
the filter element may be varied so as to yield the desired balance
of performance characteristics for the filter element, as will be
recognized by those skilled in the art. Filter materials in tow
form can be processed and manufactured into filter rods using known
techniques. Filter materials in sheet-like or web form can be
formed into filter rods using techniques described in U.S. Pat. No.
4,807,809 to Pryor et al., and U.S. Pat. No. 5,074,320 to Jones,
Jr. et al. Filter materials also can be formed into rods using a
rod-making unit (for example, from Molins Tobacco Machinery, Ltd.
of Bucks, United Kingdom).
[0103] The porous filter material may contain various additional
minor components. These components may include pigments, dyes,
preservatives, antioxidants, defoamers, solvents, lubricants,
waxes, oils, resins, adhesives, and other materials, as are known
in the art.
[0104] In a preferred embodiment, the smoking article is provided
with a cavity filter composed of two cellulose acetate segments
separated by a cavity containing activated charcoal, wherein the
filter segments are wrapped in a paper plug wrap. The plug wrap may
be provided with perforations in the cellulose acetate segment
adjacent to the tobacco rod if air dilution is desired, for
example, for low or ultra-low tar cigarettes. The cellulose acetate
segment adjacent to the tobacco rod is preferably about 9 mm in
length, the mouth end segment is preferably 11 mm in length, and
the cavity is preferably 5 mm in length. The cavity is preferably
substantially filled. Substantially filled generally refers to a
cavity segment wherein more than about 95 vol. % is filled with
packed particles, preferably more than about 96, 97, 98, or 99 vol.
% is filled with packed particles, and most preferably about 100
vol. % is filled with packed particles. However, in certain
embodiments it may be desirable for the cavity to be less than
substantially filled, for example, less than about 95, 94, 93, 92,
91, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15,
10, or 5 vol. % or less. In a preferred embodiment, the cavity is
substantially filled with one type of activated charcoal. However,
in certain other embodiments the activated charcoal may constitute
a mixture of activated charcoals (for example, charcoals of varying
particle size or source), or the activated charcoal may be mixed or
combined with one or more inert ingredients, such as magnesium
silicate (available as CAVIFLEX.TM. and SEL-X-4.TM. from
Baumgartner, Inc. of Melbane, N.C.), inert carbon, or semolina.
Most preferably, the cavity segment contains 0.1 g of a single type
of activated charcoal as the sole component in a 5 mm long cavity
segment of filter. In various embodiments various types of
activated charcoal or carbon prepared from different starting
materials, having different surface area and particle size, or
having different properties may be preferred. Suitable activated
carbons, including specialty activated carbons, may be obtained
from Calgon Carbon Corporation of Pittsburgh, Pa.
Additives
[0105] Additional components, as are known in the art, may also be
added to the smokable material, or may be contained within the
filter, the tobacco rod, or other components of the smoking
articles of preferred embodiments. Nonlimiting examples of such
components include tobacco extracts, lubricants, flavorings, and
the like. These additional components preferably do not react with
the metallic or carbonaceous particles or nitrate or nitrite source
on the smoking material in such a way as to substantially reduce
their effectiveness in reducing PAHs or other undesirable
components in smoke during use. To the extent that such reactions
do occur, they can be compensated for by alterations in the
concentration of the metallic or carbonaceous particles, the
nitrate or nitrite source, and/or the additional components.
[0106] The filter element optionally can include a tobacco or
flavor extract in intimate contact with the filter material. If
desired, the tobacco or flavor extract can be spray dried and/or
subjected to heat treatment. The filter element prior to smoking
may include less than about 10% tobacco or flavor extract to more
than 50% percent tobacco or flavor extract, based on the total dry
weight of the filter element and extract. In some embodiments, the
tobacco Filter elements typically include a lubricating substance
in intimate contact with the filter material. Normally, prior to
smoking the cigarette, the filter element includes at least about
0.1 percent lubricating substance, based on the weight of the
filter material of that segment. The lubricating substance can be a
low molecular weight liquid (for example, glycerine) or a high
molecular weight material (for example, an emulsifier).
[0107] Flavorants such as menthol can be incorporated into the
cigarette using techniques familiar to the skilled artisan. If
desired, flavor additives such as organic acids can be incorporated
into the cigarette as additives to cut filler. See, for example,
U.S. Pat. No. 4,830,028 to Lawson et al. The metallic or
carbonaceous particles and nitrate or nitrite source are preferably
applied to the cut filler prior to addition of flavorants or flavor
extract is between 15%, 20%, 25% or 30% and 35%, 40%, or 45%, of
the total dry weight of the filter element and the extract.
The Smokable Material
[0108] The metallic or carbonaceous particles and nitrate or
nitrite source may be applied to any suitable smokable material.
Examples of preferred smokable materials are the tobaccos that
include but are not limited to Oriental, Virginia, Maryland, and
Burley tobaccos, as well as the rare and specialty tobaccos. The
tobacco plant may be a variety produced through conventional plant
breeding methods, or may be a genetically engineered variety. Low
nicotine and/or low TSNA tobacco varieties, including genetically
engineered varieties, are especially preferred. The tobacco may be
cured using any acceptable method, including, but not limited to,
flue-curing, air-curing, sun-curing, and the like, including curing
methods resulting in low nitrosamine levels, such as the curing
methods disclosed in U.S. Pat. No. 6,202,649 and U.S. Pat. No.
6,135,121 to Williams.
[0109] Generally, the tobacco material is aged. The cured or
uncured tobacco may be subjected to any suitable processing step,
including, but not limited to, microwave or other radiation
treatment, treatment with ultraviolet light, or extraction with an
aqueous or nonaqueous solvent.
[0110] The tobacco can be in the form of tobacco laminae, processed
tobacco stems, reconstituted tobacco material, volume expanded
tobacco filler, or blends thereof. The type of reconstituted
tobacco material can vary. Certain suitable reconstituted tobacco
materials are described in U.S. Pat. No. 5,159,942 to Brinkley et
al. Certain volume expanded tobacco materials are described in U.S.
Pat. No. 5,095,922 to Johnson et al. Blends of the aforementioned
materials and tobacco types can be employed. Exemplary blends are
described in U.S. Pat. No. 5,074,320 to Jones, Jr. et al. Other
smokable materials, such as those smokable materials described in
U.S. Pat. No. 5,074,321 to Gentry et al., and U.S. Pat. No.
5,056,537 to Brown et al., also can be employed.
[0111] The smokable materials generally are employed in the form of
cut filler as is common in conventional cigarette manufacture. For
example, the smokable filler material can be employed in the form
of pieces, shreds or strands cut into widths ranging from about 1/5
inch (5 mm) to about 1/60 inch (0.04 mm), preferably from about
1/20 inch (1.3 mm) to about 1/40 inch (0.6 mm). Generally, such
pieces have lengths between about 0.25 inch (6 mm) and about 3
inches (76 mm). In certain embodiments, however, it may be
preferred to use cut filler having widths more than about 1/5 inch
(5 mm) or less than about 1/60 inch (0.04 mm), and lengths less
than about 0.25 inch (6 mm) or more than about 3 inches (76
mm).
[0112] The smokable material can have a form (for example, a blend
of smokable materials, such as a blend of various types of tobacco
in cut filler form) having a relatively high nicotine content. Such
a smokable material typically has a dry weight nicotine content
above about 2.0%, 2.25%, 2.5%, 2.75%, or 3.0% or more. Such
smokable materials are described in U.S. Pat. No. 5,065,775 to
Fagg.
[0113] Alternatively, the smokable material can have a form having
a relatively low or negligible nicotine content. Such a smokable
material typically has a dry weight nicotine content below about
1.5%, 1.25%, 1.0%, 0.75%, 0.5%, 0.1%, 0.05% or less. Tobacco having
a relatively low nicotine content is described in U.S. Pat. No.
5,025,812 to Fagg et al.
[0114] As used herein, the term "dry weight nicotine content" in
referring to the smokable material is meant the mass alkaloid
nicotine as analyzed and quantitated by spectroscopic techniques
divided by the dry weight of the smokable material analyzed. See,
for example, Harvey et al., Tob. Sci., Vol. 25, p. 131 (1981).
[0115] In a preferred embodiment, the smokable material constitutes
a tobacco product obtained from tobacco plants that are
substantially free of nicotine and/or tobacco-specific nitrosamines
(TSNAs). Tobaccos that may be substantially free of nicotine or
TSNAs may be produced by interrupting the ability of the plant to
synthesize nicotine using genetic engineering. Copending
provisional application Ser. No. 60/297,154 filed Jun. 8, 2001,
filed Jun. 8, 2001 and WO9856923 to Conkling et al. (both
incorporated herein by reference in their entirety) describe
tobacco that is substantially free of nicotine and TSNAs that is
made by exposing at least one tobacco cell of a selected variety to
an exogenous DNA construct having, in the 5' to 3' direction, a
promoter operable in a plant cell and DNA containing a portion of a
DNA sequence that encodes an enzyme in the nicotine synthesis
pathway. The DNA is operably associated with the promoter, and the
tobacco cell is transformed with the DNA construct, the transformed
cells are selected, and at least one transgenic tobacco plant is
regenerated from the transformed cells. The transgenic tobacco
plants contain a reduced amount of nicotine and/or TSNAs as
compared to a control tobacco plant of the same variety. In
preferred embodiments, DNA constructs having a portion of a DNA
sequence that encodes an enzyme in the nicotine synthesis pathway
may have the entire coding sequence of the enzyme, or any portion
thereof.
[0116] In a preferred embodiment, the smokable material constitutes
a tobacco product obtained from tobacco plants that have reduced
nicotine content and/or TSNAs such as those described in copending
provisional application Ser. No. 60/229,198, filed Aug. 30, 2000
(incorporated herein by reference in its entirety).
[0117] Tobacco products having specific amounts of nicotine and/or
TSNAs may be created through blending of low nicotine/TSNA tobaccos
such as those described above with conventional tobaccos. Some
blending approaches begin with tobacco prepared from varieties that
have extremely low amounts of nicotine and/or TSNAs. By blending
prepared tobacco from a low nicotine/TSNA variety (for example,
undetectable levels of nicotine and/or TSNAs) with a conventional
tobacco (for example, Burley, which has 30,000 parts per million
(ppm) nicotine and 8,000 parts per billion (ppb) TSNA; Flue-Cured,
which has 20,000 ppm nicotine and 300 ppb TSNA; and Oriental, which
has 10,000 ppm nicotine and 100 ppb TSNA), tobacco products having
virtually any desired amount of nicotine and/or TSNAs can be
manufactured. Tobacco products having various amounts of nicotine
and/or TSNAs can be incorporated into tobacco use cessation kits
and programs to help tobacco users reduce or eliminate their
dependence on nicotine and reduce the carcinogenic potential.
[0118] For example, a step 1 tobacco product can constitute
approximately 25% low nicotine/TSNA tobacco and 75% conventional
tobacco; a step 2 tobacco product can constitute approximately 50%
low nicotine/TSNA tobacco and 50% conventional tobacco; a step 3
tobacco product can constitute approximately 75% low nicotine/TSNA
tobacco and 25% conventional tobacco; and a step 4 tobacco product
can constitute approximately 100% low nicotine/TSNA tobacco and 0%
conventional tobacco. A tobacco use cessation kit can include an
amount of tobacco product from each of the aforementioned blends to
satisfy a consumer for a single month program. That is, if the
consumer is a one pack a day smoker, for example, a single month
kit provides 7 packs from each step, a total of 28 packs of
cigarettes. Each tobacco use cessation kit may include a set of
instructions that specifically guide the consumer through the
step-by-step process. Of course, tobacco products having specific
amounts of nicotine and/or TSNAs may be made available in
conveniently sized amounts (for example, boxes of cigars, packs of
cigarettes, tins of snuff, and pouches or twists of chew) so that
consumers could select the amount of nicotine and/or TSNA they
individually desire. There are many ways to obtain various low
nicotine/low TSNA tobacco blends using the teachings described
herein and the following is intended merely to guide one of skill
in the art to one possible approach.
[0119] To obtain a step 1 tobacco product, which is a 25% low
nicotine/TSNA blend, prepared tobacco from an approximately 0 ppm
nicotine/TSNA tobacco can be mixed with conventional Burley,
flue-cured, or Oriental in a 25%/75% ratio respectively to obtain a
Burley tobacco product having 22,500 ppm nicotine and 6,000 ppb
TSNA, a flue-cured product having 15,000 ppm nicotine and 225 ppb
TSNA, and an Oriental product having 7,500 ppm nicotine and 75 ppb
TSNA. Similarly, to obtain a step 2 product, which is 50% low
nicotine/TSNA blend, prepared tobacco from an approximately 0 ppm
nicotine/TSNA tobacco can be mixed with conventional Burley,
flue-cured, or Oriental in a 50%/50% ratio respectively to obtain a
Burley tobacco product having 15,000 ppm nicotine and 4,000 ppb
TSNA, a flue-cured product having 10,000 ppm nicotine and 150 ppb
TSNA, and an Oriental product having 5000 ppm nicotine and 50 ppb
TSNA. Further, a step 3 product, which is a 75%/25% low
nicotine/TSNA blend, prepared tobacco from an approximately 0 ppm
nicotine/TSNA tobacco can be mixed with conventional Burley,
flue-cured, or Oriental in a 75%/25% ratio respectively to obtain a
Burley tobacco product having 7,500 ppm nicotine and 2,000 ppb
TSNA, a flue-cured product having 5,000 ppm nicotine and 75 ppb
TSNA, and an Oriental product having 2,500 ppm nicotine and 25 ppb
TSNA.
[0120] It is appreciated that tobacco products are often a blend of
many different types of tobaccos, which were grown in many
different parts of the world under various growing conditions. As a
result, the amount of nicotine and TSNAs may differ from crop to
crop. Nevertheless, by using conventional techniques one can easily
determine an average amount of nicotine and TSNA per crop used to
create a desired blend. By adjusting the amount of each type of
tobacco that makes up the blend one of skill can balance the amount
of nicotine and/or TSNA with other considerations such as
appearance, flavor, and smokability. In this manner, a variety of
types of tobacco products having varying level of nicotine and/or
nitrosamine, as well as, appearance, flavor and smokability can be
created. Such types of tobacco products may behave in similar
manners when the metallic or carbonaceous particles and nitrate or
nitrite source of preferred embodiments are applied thereto.
[0121] While in the preferred embodiments the metallic or
carbonaceous particles and nitrate or nitrite source are applied to
a smokable material including tobacco, any other smokable materials
may preferred in other embodiments. For example, the metallic or
carbonaceous particles and nitrate or nitrite source may be applied
to smokable plant materials as are commonly preferred in various
herbal smoking materials. Mullein and Mugwort are commonly
preferred base materials in blends of herbal smoking materials.
Some other commonly preferred plant materials that are also
smokable materials include Willow bark, Dogwood bark, Pipsissewa,
Pyrola, Kinnikinnik, Manzanita, Madrone Leaf, Blackberry,
Raspberry, Loganberry, Thimbleberry, and Salmonberry.
[0122] The catalyst systems of preferred embodiments may be applied
to any smokable material in order to reduce the amounts of certain
undesired components in the smoke produced by burning the smokable
material. However, the degree of reduction in the level of one or
more of such undesired components, as well as the resulting amount
of such undesired components may vary depending upon the type of
smokable material used.
The Wrapping Material
[0123] The wrapping material which circumscribes the charge of
smokable material can vary. Examples of suitable wrapping materials
are cigarette paper wrappers available from Schweitzer-Mauduit
International in Alpharetta, Ga. Cigarette paper wraps the column
of tobacco in a cigarette and can be made from flax, wood, or a
combination of fibers. Certain properties such as basis weight,
porosity, opacity, tensile strength, texture, ash appearance,
taste, brightness, good gluing, and lack of dust are selected to
provide optimal performance in the finished product, as well as to
meet runnability standards of the high-speed production processes
preferred by cigarette manufacturers.
[0124] A more porous paper is one that allows air to easily pass
into a cigarette. Porosity is measured in Coresta units and can be
controlled to determine the rate and direction of airflow through
the cigarette. The higher the number of Coresta units, the more
porous the paper. Tar and nicotine yields are commonly controlled
without altering the flavor of the cigarette through the choice of
paper. The use of highly porous papers can help create lower tar
levels in the cigarette. Higher paper porosity increases the
combustibility of a cigarette by adding more air to the process,
which increases the heat and the burning rate. A higher burn rate
may lower the number of puffs that a smoker takes per cigarette.
Papers having porosities up to 200 Coresta units or higher are
generally preferred, however different kinds of cigarettes may use
papers of preferred porosities. For example, American-blend
cigarettes typically use 40 to 50 Coresta unit papers. Flue-cured
tobacco cigarettes, which burn slower, generally use higher
porosities, ranging from 60 to 80 Coresta unit papers. Higher
porosities may be obtained by electronically perforating (EP) the
paper.
[0125] Cigarette papers are available that are prepared from
various base fibers. Flax and wood are commonly preferred base
fibers. In addition to 100% flax and 100% wood papers, papers are
also available with flax and wood fibers mixed in various ratios.
Wood based papers are widely preferred because of their low cost,
however certain consumers prefer the taste of flax based
papers.
[0126] Suitable cigarette papers may be obtained from RFS (US)
Inc., a subsidiary of privately-held PURICO (IOM) Limited of the
United Kingdom, which is the current owner of P. H. Glatfelter
Company's Ecusta mill which manufactures tobacco papers. In
preferred embodiments, a paper having a porosity of about 26
Coresta EP to 90 Coresta EP is preferred. Suitable papers include
Number 409 papers having a porosity of 26 Coresta and 0.85% citrate
content, and Number 00917 papers having a porosity of 26 Coresta
EP. However, in certain embodiments, it may be preferred to use a
paper having a lower air permeability, for example, a paper that
has not been subjected to electronic perforation and which has a
low inherent porosity, for example, less than 26 Coresta.
[0127] In preferred embodiments, the cigarette paper is suitable
for use in "self-extinguishing" cigarettes. Examples of cigarette
papers suitable for use in self-extinguishing cigarettes include,
for example, papers saturated with a citrate or phosphate fire
retardant or incorporating one or more fire retardant bands along
the length of the paper. Such papers may also be thicker papers of
reduced flammability.
[0128] Wrapping materials described in U.S. Pat. No. 5,220,930 to
Gentry may be preferred in certain embodiments. More than one layer
of circumscribing wrapping material can be employed, if desired.
See, for example, U.S. Pat. No. 5,261,425 to Raker et al. Other
wrapping material includes plug wrap paper and tipping paper. Plug
wrap paper wraps the outer layer of the cigarette filter plug and
holds the filter material in cylindrical form. Highly porous plug
wrap papers are preferred in the production of filter-ventilated
cigarettes.
[0129] Tipping paper joins the filter element with the tobacco rod.
Tipping papers are typically made in white or a buff color, or in a
cork pattern, and are both printable and glueable at high speeds.
Such tipping papers are used to produce cigarettes that are
distinctive in appearance, as well as to camouflage the use of
activated carbon in the filter element. Pre-perforated tipping
papers are commonly preferred in filter-ventilated cigarettes.
[0130] In the case of cigars, reconstituted tobacco wrapper is
often wrapped around the outside of machine-made cigars to provide
a uniform, finished appearance. The wrapper material can
incorporate printed veins to give the look of natural tobacco leaf.
Such wrapper material is manufactured utilizing tobacco leaf
by-products. Reconstituted tobacco binder holds the "bunch" or
leaves of tobacco in a cylindrical shape during the production of
machine-made cigars. It is also manufactured utilizing tobacco leaf
by-products.
[0131] An extremely small amount of a sideseam adhesive is
preferred to secure the ends of the cigarette paper wrapper around
the tobacco rod (and filter element, if present). Any suitable
adhesive may be used. In a preferred embodiment, the sideseam
adhesive is an emulsion of ethylene vinyl acetate copolymer in
water.
[0132] The cigarette wrapper may include extremely small amounts of
inks containing oils, varnishes, pigments, dyes, and processing
aids, such as solvents and antioxidants. Ink components may include
such materials as linseed varnish, linseed oil polymers, white
mineral oils, clays, silicas, natural and synthetic pigments, and
the like, as are known in the art.
Smoking Articles
[0133] The smoking articles of the preferred embodiments may have
various forms. Preferred smoking articles may be typically
rod-shaped, including, for example, cigarettes and cigars. In
addition, the smoking article may be tobacco for a pipe. For
example, the smoking article can have the form of a cigarette
having a smokable material (for example, tobacco cut filler)
wrapped in a circumscribing paper wrapping material. Exemplary
cigarettes are described in U.S. Pat. No. 4,561,454 to Guess. In a
preferred embodiment, the smoking article is a cigarette having a
smokable filter material or tobacco rod.
[0134] In another preferred embodiment, a cigarette is provided
which yields relatively low levels of "tar" per puff on average
when smoked under FTC smoking conditions (for example, an "ultra
low tar" cigarette).
[0135] In another preferred embodiment, a cigarette is provided
having a smokable filler material or tobacco rod having a
relatively low or negligible nicotine content, and a filter
element.
[0136] In another preferred embodiment, a cigarette is provided
having a smokable filler material or tobacco rod having a
relatively low TSNA content, and a filter element.
[0137] The amount of smokable material within the tobacco rod can
vary, and can be selected as desired. Packing densities for tobacco
rods of cigarettes are typically between about 150 and about 300
mg/cm.sup.3, and are preferably between about 200 and about 280
mg/cm.sup.3, however, higher or lower amounts may be preferred for
certain embodiments.
[0138] Typically, a tipping material circumscribes the filter
element and an adjacent region of the smokable rod such that the
tipping material extends about 3 mm to about 6 mm along the length
of the smokable rod. Typically, the tipping material is a
conventional paper tipping material. The tipping material can have
a porosity which can vary. For example, the tipping material can be
essentially air impermeable, air permeable, or can be treated (for
example, by mechanical or other perforation techniques) so as to
have a region of perforations, openings or vents, thereby providing
a means for providing air dilution to the cigarette. The total
surface area of the perforations and the positioning of the
perforations along the periphery of the cigarette can be varied in
order to control the performance characteristics of the
cigarette.
[0139] The mainstream cigarette smoke may be diluted with air from
the atmosphere via the natural porosity of the cigarette wrapper
and/or tipping material, or via perforations, openings, or vents in
the cigarette wrapper and/or tipping material. Air dilution means
may be positioned along the length of the cigarette, typically at a
point along the filter element which is at a maximum distance from
the extreme mouth-end thereof. The maximum distance is dictated by
factors such as manufacturing constraints associated with the type
of tipping employed and the cigarette manufacturing apparatus and
process. For example, for a filter element having a 27 mm length,
the maximum distance may be between about 23 mm and about 26 mm
from the extreme mouth-end of the filter element. In a preferred
aspect, the air dilution means is positioned toward the extreme
mouth-end of the cigarette relative to the smoke-altering filter
segment. For example, for a filter element having a 27 mm length
including a smoke-altering filter segment of 12 mm length and a
mouth-end segment of 15 mm, a ring of air dilution perforations can
be positioned either 13 mm or 15 mm from the extreme mouth-end of
the filter element.
[0140] As used herein, the term "air dilution" is the ratio
(generally expressed as a percentage) of the volume of air drawn
through the air dilution means to the total volume of air and smoke
drawn through the cigarette and exiting the extreme mouth-end
portion of the cigarette. For air diluted or ventilated cigarettes,
the amount of air dilution can vary. Generally, the amount of air
dilution for an air-diluted cigarette is greater than about 10
percent, typically greater than about 20 percent, and often greater
than about 30 percent. Typically, for cigarettes of relatively
small circumference (namely, about 21 mm or less) the air dilution
can be somewhat less than that of cigarettes of larger
circumference. The upper limit of air dilution for a cigarette
typically is less than about 85 percent, more frequently less than
about 75 percent. Certain relatively high air diluted cigarettes
have air dilution amounts of about 50 to about 75 percent, often
about 55 to about 70 percent.
[0141] Cigarettes of certain embodiments may yield less than about
0.9, often less than about 0.5, and usually between about 0.05 and
about 0.3 FTC "tar" per puff on average when smoked under FTC
smoking conditions (FTC smoking conditions include 35 ml puffs of 2
second duration separated by 58 seconds of smolder). Such
cigarettes are "ultra low tar" cigarettes which yield less than
about 7 mg FTC "tar" per cigarette. Typically, such cigarettes
yield less than about 9 puffs, and often about 6 to about 8 puffs,
when smoked under FTC smoking conditions. While "ultra low tar"
cigarettes are generally preferred, in certain embodiments,
however, cigarettes providing less than about 0.05 or more than
about 0.9 FTC "tar" per puff are contemplated.
[0142] In certain embodiments, cigarettes yielding a low or
negligible amount of nicotine are provided. Such cigarettes
generally yield less than about 0.1, often less than about 0.05,
frequently less than about 0.01, and even less than about 0.005 FTC
nicotine per puff on average when smoked under FTC smoking
conditions. In other embodiments, a cigarette delivering higher
levels of nicotine may be desired. Such cigarettes may deliver
about 0.1, 0.2, 0.3, or more FTC nicotine per puff on average when
smoked under FTC smoking conditions.
[0143] Cigarettes yielding a low or negligible amount of nicotine
may yield between about 1 mg and about 20 mg, often about 2 mg to
about 15 mg FTC "tar" per cigarette; and may have relatively high
FTC "tar" to FTC nicotine ratios of between about 20 and about
150.
[0144] Cigarettes of the preferred embodiments may exhibit a
desirably high resistance to draw, for example, a pressure drop of
between about 50 and about 200 mm water pressure at 17.5 cc/sec of
air flow. Typically, pressure drop values of cigarettes are
measured using instrumentation available from Cerulean (formerly
Filtrona Instruments and Automation) of Milton Keynes, United
Kingdom. Cigarettes of preferred embodiments preferably exhibit
resistance to draw values of about 70 to about 180, more preferably
about 80 to about 150 mm water pressure drop at 17.5 cc/sec of
airflow.
[0145] Cigarettes of preferred embodiments may include a
smoke-altering filter segment. The smoke-altering filter segment
may reduce one or more undesirable components in the smoke, and/or
may provide an enhanced tobacco smoke flavor, a richer smoking
character, enhanced-mouthfeel and increased smoking satisfaction,
as well as improvement of the perceived draw characteristics of the
cigarette.
EXAMPLES
Preparation of Suspension of Palladium Particles in Solution of
Magnesium Nitrate
[0146] 12 g of low invert sugar is added to 94 ml of deionized
ultrafiltered water and the mixture is heated to a temperature
between 70.degree. C. and 80.degree. C. with constant mixing in a
glass-lined vessel equipped with a heating jacket. 0.977 g of
(NH.sub.4).sub.2PdCl.sub.4 is added to the reaction mixture, which
is stirred constantly for three hours while maintaining the
temperature between 70.degree. C. and 80.degree. C. After three
hours, conversion of 63-70% of the palladium ion to palladium metal
is achieved. Particle size measurements conducted using X-Ray
Diffraction (XRD) indicate the presence of crystalline particles of
approximately 100 nm in diameter. Laser scattering measurements
indicate the presence of particles of approximately 1 .mu.m in
diameter. While not wishing to be limited to any particular
mechanism, it is believed that the crystalline particles of
approximately 100 nm in diameter cluster together to form larger
particles of approximately 1 .mu.m in diameter.
[0147] After the allotted time, 19.88 g (70%)
Mg(NO.sub.3).sub.2-6H.sub.2O is added to the suspension of
palladium particles. The suspension is then applied to
approximately 0.45 kg (approximately one pound) of cut tobacco
filler.
Palladium Particle Size Analysis
[0148] One way of determining if the catalyst is properly prepared
is to determine the particle size of the palladium in each reaction
vessel after the reaction has occurred and to ensure that the mean
and mode fall within a predetermined range.
[0149] Into a 5 L reaction vessel equipped with a glass stirring
mechanism and immersed thermocouple with digital temperature
readout/control were placed suitable amounts of deionized-ultra
filtered water and low invert sugar for producing 5 L of solution
as described in the previous example. The solution was heated to
70.degree. C. with constant stirring. Upon temperature
stabilization at 70.degree. C., a suitable amount of palladium salt
in the form of (NH.sub.4).sub.2PdCl.sub.4 was added to the
water/sugar solution.
[0150] Catalyst samples were taken from the reaction vessel at the
first and third hours of the reaction and before the catalyst
solution was sprayed on the tobacco. Catalyst samples
(approximately 20 ml) were taken from a depth of 61 cm in the
reaction vessel by using a clean elongated glass pipette. The
samples were then placed into a centrifuge tube and agitated prior
to analysis.
[0151] The percent conversion of the palladium salt to palladium
metal was monitored using a Perkin-Elmer graphite furnace atomic
absorption spectrometer. The particle size of the formed palladium
metal particles was monitored by a Coulter LS230 light scattering
instrument that detects particle sizes ranging from 0.04 .mu.m to
2000 .mu.m. The samples were pipetted into a Coulter LS 230
particle size analyzer until the obscuration percentage was above
8% and the Polarization Intensity Differential Scanning (PIDS)
value was between 45 and 55%. Each sample was analyzed three times
before the observation was made and the mean and mode were
determined.
[0152] Table 1 below presents typical results for mean and mode of
palladium particles in various catalyst batches prepared by the
process described in previous examples and determined using an LS
230 Analyzer and the method described above. FIG. 1 provides a
typical catalyst chromatogram providing palladium particle
diameters (.mu.m) in a typical reducing solution after
reaction.
TABLE-US-00001 TABLE 1 Palladium Size Mean and Mode for Different
Catalyst Samples Date Catalyst number Mean Mode Oct. 16, 2001
1A299010650 6.108 7.083 Oct. 16, 2001 28289010430 6.279 7.083 Oct.
17, 2001 28290011300 6.662 7.775 Oct. 18, 2001 28291011020 9.630
10.290 Oct. 18, 2001 2A91010700 7.558 8.536 Oct. 19, 2001
1A292010450 7.758 8.536 Oct. 19, 2001 28292010945 7.597 8.536 Oct.
22, 2001 3A295011130 8.409 7.775 Oct. 20, 2001 1A293010650 6.261
7.083 Oct. 25, 2001 1A298011150 7.868 8.536
[0153] The catalyst mean and mode preferably fall within the range
of 4.04-14.74 .mu.m for the mean and 6.55-12.33 .mu.m for the mode
in order for the catalyst batch to be released and sprayed. If
either the mode or the mean is outside the range, the catalyst may
be rejected, depending upon how far outside the range the value
falls. However if the mean and the mode are both outside the
predetermined ranges, the catalyst is generally rejected and is not
sprayed onto the tobacco.
Optimization of Catalyst Addition Process
[0154] L of palladium catalyst solution prepared as described above
was sprayed onto 40 lbs. (approximately 18 kg) of tobacco. A hand
held spraying wand connected to a dual-head ceramic piston pump was
used to transfer the palladium metal suspension onto the tobacco.
The solution was applied to ten pounds (approximately 4.5 kg) of
tobacco at a time using a ten pound tobacco tumbler in order to
obtain even coverage on the tobacco. Forty pounds of tobacco can
typically be adequately treated with 5 L of palladium metal
suspension according to the formulation in the preceding
example.
[0155] The wet tobacco was then placed onto the manufacturing
feeder belts and fed through the tobacco dryer to bring the
moisture level down to approximately 13.5%. The dried tobacco was
then taken to a cigarette making machine and hand fed into the
machine to make enough cigarette samples for chemical analysis. The
treated cigarettes were conditioned and smoked on Borgwaldt smoking
machines and the PAH/TSNA/Phenolic component(s) of the total
particulate matter were extracted and analyzed to determine what
change had taken place upon modification of the tobacco
additive.
[0156] Instrumentation that utilizes the optical properties of
materials on the micron and sub-micron scale was used to measure
the particle size and size distribution of particles suspended in
solution. When low invert sugar is used as the reducing agent,
palladium metal particle sizes on the order of 7-9 microns are
primarily formed. X-ray powder diffraction experiments performed on
the palladium metal suggest that the size of the palladium
particles is on the order of 100 nanometers. Thus, a discrepancy of
over an order of magnitude exists when measuring the palladium
particles via X-ray diffraction versus optical measurements.
[0157] Optical microscopy of palladium particles taken directly
from the reacting solution suggests that the size discrepancy may
be attributed to the fact that the low invert sugar contains
"globules" (most probably entangled polysaccharides) that exist in
the 7-9 micron size range at 70.degree. C. The sugar globules were
observed to have palladium crystallites either stuck to the outside
or trapped between sugar globules. This suggests that the effective
surface area for a specified amount of palladium may be
significantly reduced due to adhesion or trapping of the palladium
crystallites on or in the sugar globules. Therefore, it is
preferred to maximize the surface area of the palladium metal in
the catalyst system so as to provide the maximum reduction of
carcinogens in tobacco smoke.
[0158] Several options for increasing the surface area of the
palladium metal particles are available. The first option is to
utilize surfactants in an attempt to break apart the large sugar
particles that exist in the low invert sugar solution.
Tetradodecylammonium bromide surfactant (TDABr) has been used to
produce inverse microemulsions of nanometer scale palladium metal
in organic solvents such as tetrahydrofuran (THF) and ethanol. The
more common and less expensive surfactant cetyltrimethylammonium
bromide (CTAB) may also be used, however any suitable surfactant
may be used as instead of the specific surfactants enumerated
herein. In the case of water/low invert sugar solutions, the
surfactant may break apart the large sugar particles and thereby
reduce the size of the palladium clusters. In a water/ethanol
solution, ethanol may be used as the reducing agent, which requires
higher temperatures, and CTAB or another surfactant may be utilized
in order to form the inverse microemulsions required for the
formation of nanoscale palladium particles. Ethanol or other
alcohols may be used as reducing reagents in water, but such
palladium salt solutions are generally dilute and high temperatures
may be preferred.
Palladium Ion Conversion
[0159] The effectiveness of the catalyst is related to the
distribution of the palladium metal over the tobacco itself. Given
a specific amount of palladium, the effectiveness is related to
both the particle size of the palladium metal and the percent
conversion of the palladium starting material to palladium metal.
The conversion reaction proceeds relatively slowly at low
temperatures. When the temperature of the reaction is held at about
70.degree. C., the reaction is essentially complete after 3
hours.
[0160] To study this reaction, the percent conversion and particle
size of the palladium metal was observed in many different
reactions. Some examples of variations among these experiments
included changing the temperature of the reaction, using varying
amounts of reactants along with varied concentrations, and allowing
the reaction to proceed for various lengths of time.
[0161] Catalyst samples prepared as described above were collected
from a reaction vessel at 30 minute intervals, quenched in a dry
ice/acetone bath and brought to room temperature. These samples
were centrifuged at 3400 rpm for 10 minutes to precipitate the
palladium metal. The supernatants were collected and centrifuged
again. A one-milliliter aliquot of this solution underwent a series
of dilutions in preparation for injection into the atomic
absorption analyzer. The sample was analyzed for concentration of
palladium ions on a Perkin-Elmer atomic absorption analyzer
equipped with a graphite furnace and Zeeman background correction.
The data was quantified to show a percent conversion of palladium
ions into palladium metal. FIG. 2 shows the percent conversion of
palladium over a 5 hour reaction at 70.degree. C. with samples
analyzed every hour. Based on the results shown in FIG. 2, the
maximum conversion occurs at 5 hours with a 70% conversion of
palladium ions into palladium metal by that time. There is a steady
increase in percent conversion for the first three hours of the
reaction, while the percent conversion levels off after the initial
three hours. These results suggest that the reaction may yield
higher percent conversions the longer the reaction is allowed to
proceed.
Reduction in PAH Levels
[0162] Experiments were conducted to compare the levels of PAHs in
smoke from cigarettes containing tobacco incorporating palladium
particles and magnesium nitrate to those of comparable cigarettes
not containing the catalyst system. A catalyst system was prepared
as described in the first Example, and applied to a Southern
Commercial tobacco blend. The tobacco was fashioned into unfiltered
cigarettes (Hauni Baby cigarettes, Pd catalyst, not filtered;
smoked cigarettes were selected based on a 5% tolerance level of
the average of 200).
[0163] Catalyst-containing cigarettes and cigarettes without
catalyst were smoked and the reduction in levels of certain PAHs,
including phenanthrene, 2-methylanthracene, pyrene, chrysene,
benzo[b/k]fluoranthene, and benzo[a]pyrene for the
catalyst-containing cigarettes were measured using standard
methodology well known in the art. Test results are presented in
Table 2 below. The results demonstrate a substantial reduction in
the levels of PAHs when the catalyst system is present, including a
reduction of over 50% for 2-methylanthracene. The smallest
reduction was about 29%, observed for benzo[b/k]fluoranthene.
TABLE-US-00002 TABLE 2 Commercial Blend Effect on PAH level
compared % PAH to cigarette without catalyst change error
phenanthrene reduced 31.01 1.40 2-methylanthracene reduced 51.61
1.24 pyrene reduced 39.18 1.02 chrysene reduced 41.44 1.22
benzo[b/k]fluoranthene reduced 28.84 1.52 benzo[a]pyrene reduced
38.38 0.93 Cigarette Smoke reduced 18.75 0.83 Condensate (CSC)
Amounts:
[0164] The same catalyst system was applied to a tobacco blend
containing 22% expanded tobacco that had been cased with a special
casing that leaves out the invert sugar that is added in with the
Pd solution. The catalyst solution was sprayed on the blend and
production cigarettes were made. Reductions in PAH levels were
again measured and compared to those for the cigarettes described
above. The resulting reductions, provided in Table 3 below, were
statistically different for all PAHs except naphthalene,
dibenzofuran, anthracene, and benzo[a]pyrene. These data indicate
that nature of the tobacco blend treated may affect the degree of
reduction of certain PAHs in the resulting smoke.
TABLE-US-00003 TABLE 3 22% Expanded Tobacco Blend Effect on PAH
level compared % PAH to cigarette without catalyst change error
phenanthrene reduced 16.12 0.24 2-methylanthracene reduced 32.44
2.34 pyrene reduced 20.70 0.48 chrysene reduced 13.33 1.15
benzo[b/k]fluoranthene reduced 16.47 1.45 benzo[a]pyrene reduced
9.39 0.54 Cigarette Smoke reduced 3.15 0.05 Condensate (CSC)
Amounts:
Determination of PAHs by Mass Spectrometry
[0165] Polycyclic aromatic hydrocarbons (PAHs) are a major group of
compounds, with known carcinogenic and mutagenic activity.
Reductions in these PAHs serve as a useful indication that the
catalyst system is working in the treated product. However, there
is no standardized method reported in the literature for the
simultaneous separation and detection of multiple PAHs. In fact,
there is a large variance found for reported methods used to
analyze just one of the PAHs, namely benzo[a]pyrene. Shown in Table
4 are the average values found by several groups working with the
Kentucky reference cigarette 1R4F.
TABLE-US-00004 TABLE 4 Concentrations of B[a]P (ng/cig) - Kentucky
Reference Cigarette 1R4F Tomkins Gmeiner et al. Risner Risner
Dumont et al. Evans et al. et al. (1985) (1988) (1991) (1993)
(1993) (1997) 6.6 6.4 9.2 8.5 5.3-8.2 7.9
[0166] A new Extraction Protocol, described below, was developed
which involves various liquid extraction steps and the use of a
vacuum manifold to separate the PAHs by silica SPE cartridges. Very
reliable data was obtained from this method due to the control over
flow rate and the selective removal of several hydrocarbons.
Hydrocarbons can co-elute with the PAHs and can act to inflate the
concentrations being quantified. The standard deviations obtained
from this new method are very low.
[0167] Experiments were conducted to measure the levels of 17
different PAHs in cigarette smoke using the new Extraction
Protocol. Cigarettes (40 per sample) were smoked following the FTC
protocol. Samples were extracted from Cambridge pads using the
Extraction Protocol described below. The Extraction Protocol
enables 17 PAHs to be quantified, compared to conventional
extraction methods that only focus on benzo(a)pyrene. The
Extraction Protocol allows for high sample throughput and is highly
reproducible. Table 5 provides data on selected PAH levels for a
sample of Kentucky Reference cigarettes (IR4F) comparing a
conventional liquid extraction method and a solid extraction method
using the Extraction Protocol set forth below.
TABLE-US-00005 TABLE 5 PAH Concentrations and Standard Deviations
of Marker PAHs (1R4F) Liquid Liquid Solid Solid Marker PAHs
(ng/cig) Std. Dev. (ng/cig) Std. Dev. phenanthrene 149.42 2.26
123.17 1.29 2-methylanthracene 66.15 0.87 75.50 0.56 pyrene 38.26
3.45 38.26 0.11 chrysene 15.74 0.37 17.51 1.26
benzo[b/k]fluoranthene 10.86 0.34 10.92 0.31 benzo[a]pyrene 9.49
0.18 9.55 0.22
[0168] The benefits of the solid extraction method in comparison to
the liquid extraction method include: reduced solvent usage;
greater sample throughput; fewer cigarettes required; less labor
intensive; better reproducibility; higher recoveries; and selective
removal of contaminants. Lower standard deviations are observed for
the solid extraction, for example, acceptable standard deviations
are normally below 10, but the standard deviations for the solid
extraction method are below 2. The solid extraction method also
permits faster sample throughput. Typically, a laboratory
technician can extract four samples in approximately eight hours
using the solid extraction method, compared to the liquid
extraction method wherein only one sample could be extracted in
eight hours.
Extraction Protocol
[0169] The following equipment and supplies are typically used in
conducting the extraction protocol: (1) 10-mL test tube; Sample
vials; Kimwipes; Glass pipettes; Pipette bulbs; Methylene Chloride;
Hexanes; Buchner funnel with fritted disk; 50 ml, round bottom
flask; Silica gel cartridges (200 mesh); (2) 250 ml round bottom
flask; Silica gel (63-200 mesh); Extraction Standard; (3) 10 ml,
graduated cylinder; Medium and Small cork rings; Small RB flask
holders/stands; 100 ml graduated cylinder; Vacuum Manifold; 30 ml
separatory funnel; (2) Spatulas; Roto-vap apparatus; Dry Ice;
Acetone; Ultrasound Bath; 150 ml, Beaker; Scale; UV lamp; Pipette
gun; Solvent reservoirs; Mortar and pestle; and Ether.
[0170] The Extraction Protocol is typically performed according to
the following steps: [0171] 1.) Cigarettes (40 per sample) are
smoked following the FTC protocol. Use 2 pads (20 cigarettes smoked
per pad). Spike each pad with 100 .mu.L of Extraction Standard. Cut
the pads and place into a 250 ml beaker. Add 100 ml of acetone to
beaker. [0172] 2.) Sonicate for 15 minutes and filter contents of
beaker into 250 ml, round bottom flask fitted with Buchner funnel
with fritted disk. Rinse tip of the Buchner funnel with acetone.
Replace filter strips back into the 250 ml beaker. [0173] 3.)
Roto-vap the sample at 35.degree. C. down to approximately 1 ml of
sample. [0174] 4.) Add an additional 100 ml of acetone to 250 ml
beaker with sample. [0175] 5.) Repeat the sonication for 15 minutes
and filter contents of beaker through the same Buchner funnel into
the same 250 ml round bottom flask. Push the pads down to remove as
much solvent from the pads as possible. Remove filter pad fibers
from funnel, rinse 250 ml beaker with 5 ml of acetone, and transfer
to fritted disk. Rinse the tip of the Buchner funnel with acetone
into the 250 ml, round bottom flask. [0176] 6.) Roto-vap the sample
to approximately 1 ml at 35.degree. C. [0177] 7.) Transfer the
sample to a mortar and pestle containing 1.2 g of silica (63-200
mesh activated) dropwise with Pasteur pipette. Rinse the round
bottom flask with 1 ml of acetone and 5.times.1 ml of ether and
transfer contents to silica by pipette. Continuously grind silica
until a fine powder is produced. [0178] 8.) Once sample is
completely dry, allow silica to sit for 30 minutes to allow for
complete dryness. [0179] 9.) While sample is drying on silica, set
up the vacuum manifold and rinse ports with approximately 0.5 ml
acetone. Condition a silica gel cartridge by adding 100 ml of
hexanes to the sample cartridge and adjusting flow rate to 5
ml/min. Pull column to dryness. [0180] 10.) After the cartridges
have been conditioned, shut off the flow (not the vacuum), and
drain the vacuum manifold. [0181] 11.) Just prior to loading sample
onto column, add 8 ml hexanes to re-wet the column. Allow hexanes
to completely saturate the column and run until the last drop has
evacuated the column. [0182] 12.) Transfer sample to weigh paper
and load sample onto column making sure to distribute the sample
evenly across the top. Load sample onto column using 8.times.1 ml
hexanes. Make sure to rinse the spatula, mortar, and pestle with
the first 2 ml of hexanes. Tap column to expel air bubbles. Collect
8 ml in a test tube labeled F1. [0183] 13.) Pull an additional
3.times.4 ml of hexanes through column and collect in test tubes
labeled F2, F3, and F4. Do not let the sample run dry between
additions or washes. Rinse port with approximately 0.5 ml hexanes
when switching ports. [0184] 14.) Check for fluorescence using
Spectroline UV lamp in long wave UV mode at 365 nm. Record in
notebook which fractions fluoresce. [0185] 15.) If fluorescence is
in the final fraction (F4) add the fraction to a labeled 150 ml
beaker, rinse the test tube with 1 ml of hexane, and place under
column. Make a note of any other fractions with fluorescence in the
sample notebook. For the blank, collect all four fractions in a 150
ml beaker. [0186] 16.) Elute column with 50 ml of hexanes using
solvent reservoir. [0187] 17.) Mix 3 ml of methylene chloride and
30 ml of hexanes in a graduated cylinder. Elute 33 ml of the
mixture through the column using solvent reservoir. Rinse port with
a small amount of hexanes and collect in the previously used 150 ml
beaker. [0188] 18.) Transfer the contents of the 150 ml beaker into
a 250 ml, round bottom flask, rinsing the beaker with approximately
5 ml of hexanes. Roto-vap sample to dryness at 40.degree. C. [0189]
19.) Bring sample up in 10 ml of hexanes by Pasteur pipette by
rinsing the round bottom with 2.times.3 ml and 2.times.2 ml
increments. Add each rinse to the 30 ml separatory funnel. [0190]
20.) Extract sample with 2.5 ml of nitromethane. Shake the
separatory funnel 10 times and vent; 20 times and vent; 30 times
and vent; and 40 times before venting. Collect bottom layer in a 50
ml round bottom flask. [0191] 21.) Repeat 5 times for a total
volume of 15 ml of nitromethane. [0192] 22.) Roto-vap sample at
55.degree. C. to dryness. Do not place parafilm over round bottom.
[0193] 23.) Submit samples for analysis by gas chromatography/mass
spectroscopy (GC/MS) according to standard protocols as are known
in the art.
[0194] Carbazole samples may also be obtained by performing the
following steps. [0195] 24.) Elute column with 100 ml of
4:1=hexanes:MeCl.sub.2 using solvent reservoir. [0196] 25.)
Roto-vap to dryness at 40.degree. C. [0197] 26.) Submit labeled
sample for carbazole analysis according to standard protocols as
are known in the art.
[0198] The above-described Extraction Protocol may be performed
with various modifications, as will be apparent to those skilled in
the art. For example, solvents not enumerated herein may be
satisfactorily substituted for hexanes, ether, acetone, and
methylene chloride. Adsorbents other than silica gel may also be
acceptable for use. The method may be performed using other
equipment, different quantities of samples or reagents, different
times, or different temperatures. While GS/MS is the preferred
analytical method for determining PAH or carbazole levels, other
analytical methods as are known in the art may also be used. Other
components of cigarette smoke condensate, not enumerated herein,
which are capable of extraction using the protocol may also be
analyzed by a suitable analytical method after extraction using the
protocol or acceptable variation thereof as described above.
[0199] Numerous methods for separation or analysis of PAHs in
cigarette smoke condensate have been described in the published
literature: Forehand et al., "Analysis of polycyclic aromatic
hydrocarbons, phenols and aromatic amines in particulate phase
cigarette smoke using simultaneous distillation and extraction as a
sole sample clean-up step" Journal of Chromatography A, 2000. 898:
p. 111-124; Gmeiner et al., "Determination of seventeen polycyclic
aromatic hydrocarbons in tobacco smoke condensate" Journal of
Chromatography A, 1997. 767: p. 163-169; Arrendale et al.
"Quantitative Determination of Naphthalenes in Tobacco Smoke by Gas
Chromatography" Beitrage zur Tabakforschung International, 1980.
10(2): p. 100-105; Severson et al., "Gas Chromatography
Quantitation of Polynuclear Aromatic Hydrocarbons in Tobacco Smoke"
Analytical Chemistry, 1976. 48: p. 1866-1872; Canada,
"Determination of Benzo[.alpha.]pyrene in Mainstream Tobacco Smoke"
Official Method, 1999. T-103; Schmidt et al., "Determination of
polycyclic aromatic hydrocarbons, polycyclic aromatic sulfur and
oxygen heterocycles in cigarette smoke condensate" Fresenius Z.
Anal. Chem., 1985. 322(2): p. 213-19; Allen, "Quantitation of
polycyclic aromatic hydrocarbons" Thin Layer Chromatogr.: Quant.
Environ. Clin. Appl., [Symp], 1980. Meeting Date 1979: p. 348-62;
Robb et al., "Analysis of polycyclic hydrocarbons" Beitr.
Tabakforsch. Int., 1965. 3(4): p. 278-84; Risner, "The
determination of benzo[a]pyrene and Benz[a]anthracene in mainstream
and sidestream smoke of the Kentucky Reference cigarette 1R4F and a
cigarette which heats but does not burn tobacco: a comparison"
Beitr. Tabakforsch. Int., 1991. 15(I): p. 11-17; Grimmer et al.,
"Gas chromatographic determination of polycyclic aromatic
hydrocarbons, aza-arenes, and aromatic amines in the particle and
vapor phase of mainstream and sidestream smoke of cigarettes"
Toxicol. Lett., 1987. 35(1): p. 117-24; Severson et al., "A
chromatographic analysis for polynuclear aromatic hydrocarbons in
small quantities of cigarette smoke condensate" Beitr. Tabakforsch.
Int., 1976. 8(5): p. 273-82; Klimisch, "A rapid method for the
determination of benzo[a]pyrene, benzo[a]anthracene and chrysene in
cigarette smoke" Chromatographia (1976. 9(3): p. 119-22; Severson
et al., "Isolation, identification, and quantitation of the
polynuclear aromatic hydrocarbons in tobacco smoke"
Carcinog.--Compr. Surv., 1976. 1: p. 253-70, the contents of each
of which are incorporated herein by reference in their
entireties.
Automated PAH Analysis
[0200] PAHs can be a particularly difficult group of compounds to
deal with due to their hydrophobic nature, causing them to adsorb
everywhere, leading to losses during the sampling and storage.
Despite the advantages of the new internal extraction method
described above, it is still prone to losses of sample due to
multiple transfer steps. Also, the lack of a centralized control
over flow rate can lead to variability in column performance. The
need for a method that could address these issues led to research
into automated Solid Phase Extraction (SPE). Benefits of using
automated SPE include a reduction in analyst time and a reduction
in extraction time for the automated method.
[0201] The development of an automated method first started with
the selection of an extraction method. Two extraction methods were
optimized and evaluated for possible automation. The first method
was a scaled-down version of the extraction method described above
with 2 gram silica cartridges and a nitromethane extraction serving
as the clean-up step.
[0202] The second method was based on the work of Gmeiner et al.
and does not use any evaporation steps. The only adjustment to
Gmeiner's work was the use of a cyclohexyl cartridge instead of a
C18 cartridge. The cycylohexyl cartridge was introduced by
Moldoveanu at the 2001 Tobacco Science Research Conference and
compared to the original work by Gmeiner et al. Moldoveanu
demonstrated that the C18 cartridges were incapable of producing
the 80-90% recoveries possible with their cyclohexyl counterparts.
One difficulty with this second method, however, was that the
hydrocarbons co-elute with the PAHs. The addition of a final
nitromethane extraction step may remove the hydrocarbons.
[0203] The next step involved with automation is the selection of a
robotic system. Three different systems from Prospekt, Gilson, and
Zymark were compared. Of all three systems, the Zymark RapidTrace
appeared to be the best option based upon preliminary information
due to the ability to add modules as demand increases.
[0204] Despite the good performance of the internal extraction
method described above, an automated method is desirable for
numerous reasons. An automated method can increase sample
throughput and reduce the human error involved in such laborious
extraction techniques. The evaporation steps of the method also
present a problem due to the volatility of several smaller ring
PAHs. Evaporation steps can be minimized by an automated method and
this is significant when considering the difficulty in quantifying
compounds such as naphthalene. Finally, with the likelihood of
ever-increasing regulatory pressures, automated SPE can provide
formal documentation of how sample preparation is done, recording
in electronic form, precise details of every step of every
extraction, thereby eliminating any questions about the data
collected.
Instrumentation for Performing Analyses
[0205] In conducting various analyses, the following
instrumentation was used: three gas chromatography/mass
spectrometers (GC/MS), one liquid chromatography/mass spectrometer
(LC/MS), one liquid chromatograph, and two gas chromatographs (GC).
Two of the GC/MS systems were Agilent 5973N mass selective
detectors (MSD) with a 6890 Plus gas chromatograph. The other has
an Agilent 5973N MSD and a 6890N gas chromatograph. All three
instruments have electron ionization capability, and one also has
positive and negative chemical ionization capabilities. All have
programmable autosamplers and are run using the Agilent Chemstation
software for GC/MS's. The LC/MS system is an Agilent 1100MSD SL
with an Agilent 1100 series high performance liquid chromatograph
(HPLC). The HPLC consists of a binary pump with solvent selection
valve, a vacuum degasser, a thermostated column-switching
compartment, an autosampler, and a diode array UV-Vis
spectrophotometer. The LC system is the same system as the one
associated with the LC/MS except it has a well-plate autosampler,
which allows samples to be processed in a well-plate format. This
system also has a fluorescence detector in order to perform
analyses on catechols and various other related compounds. The GCs
are both Agilent 6890N systems. One has flame ionization detection
(FID) only and the other has FID and nitrogen-phosphorous detection
(NPD). The FID specifically detects carbon and is a robust and
reliable way to detect various organic compounds, such as nicotine.
The NPD is specific for compounds containing nitrogen or
phosphorous.
[0206] The gas chromatograph/mass spectrometers (GC/MS) were
composed of a 5973N mass selective detector (MSD) that is a
quadrapole mass analyzer and a 6890 Plus gas chromatograph (GC).
The instrument and the data analysis were run using the Agilent
Chemstation software, all of which are controlled by a Hewlett
Packard Vectra computer. The computer, GC, and MSD were all
networked together using a LAN system. The GC and MSD also had a
manual control panel on the front of the oven. A programmable
autosampler was used to inject the samples. This autosampler holds
two solvent vials to rinse the syringe needle before and/or after
the sample injection. The high vacuum system consists of a
performance turbomolecular pump. This allows for more versatility
in sample analysis because higher flow rates of the carrier gas are
possible. Also, the system pumps down from atmospheric pressure
much faster than the standard diffusion pump that can decrease
instrument down time for maintenance. The mass range is 1.6-800 amu
in 0.1 amu steps, allowing a wide range of molecules to be
analyzed. The user can either perform mass analysis in a scan mode,
choosing any mass range encompassed by the instrument's
capabilities, or selected ion monitoring (SIM) can be performed.
SIM allows the user to enter up to 50 groups of masses, with up to
30 masses per group, to be analyzed, and these groups can be set up
on a timed program to be switched automatically during the
instrument run. SIM can improve sensitivity, but may result in the
loss of capability to detect interfering compounds at the masses of
interest. All of the instruments had electron ionization (EI)
capability and can have positive and negative chemical ionization
(CI) capabilities added. Of the three instruments, two have just
EI, the other has the full complement of ionization
capabilities.
[0207] The GC oven may accommodate a wide variety of GC capillary
columns, such as a Rtx-5Sil MS column, that is 30.0 m.times.0.25 mm
ID.times.0.5 .mu.m film thickness. The oven program is as follows:
initial temperature of 65.degree. C. was ramped at 50.degree.
C./min to 95.degree. C. and held for 0.00 minutes, then ramped at
17.degree. C./min to 280.degree. C. and held for 2.00 minutes, then
a ramp of 10.00.degree. C./min to 300.degree. C. with a final ramp
of 40.degree. C./min with a hold of 8.00 min. The injector
temperature is set at 300.degree. C. with a flow rate of 1.00
ml/min of helium. The detector temperature (transfer line) is set
at 280.degree. C. A 1.0 .mu.L injection is used.
[0208] The MSD source/quadrupole temperature is set at
230/150.degree. C. The source is set to electron ionization mode.
The acquisition mode is set to scan. The MS scan parameters are as
follows: a solvent delay until 5.00 minutes then scanning from 40.0
to 450.0 amu.
[0209] PAHs may be analyzed using the GC/MS systems described
above. The quantitation is done using an internal method
calibration curve. There are ten deuterated PAHs present in the
calibration curve, which act as the internal standards. Table 6
includes a list of all of the deuterated and non-deuterated PAHs
that are present in the curve.
TABLE-US-00006 TABLE 6 Compounds in the Calibration Curve # ID Base
Peak 1) D8-acenaphthalene 160 2) naphthalene 128 3) acenaphthylene
152 4) acenaphthene 153 5) dibenzofuran 168 6) D10-fluorene 176 7)
fluorene 166 8) D10-phenanthrene 188 9) phenanthrene 178 10)
D10-anthracene 188 11) anthracene 178 12) D8-carbazole 175 13)
carbazole 167 14) D-10-fluorathrathene 212 15) 2-methylanthracene
192 16) 9-methylanthracene 192 17) fluoranthene 202 18) D10-pyrene
212 19) pyrene 202 20) 2,3-benzofluorene 216 21)
D12-benzo[a]anthracene 240 22) 1,2-benzanthracene 228 23)
D12-chrysene 240 24) chrysene 228 25) D12-benzo[a]pyrene 264 26)
benzo[b/k]fluoranthene 252 27) benzo[e]pyrene 252 28)
benzo[a]pyrene 252 29) indeno[1,2,3-cd]pyrene 276 30)
dibenz[a,h]anthracene 278 31) benzo[ghi]perylene 276
[0210] The internal standards are used to determine extraction
efficiency and to calculate the concentration of the analytes. In
order to calculate extraction efficiency, a 100% recovery standard
is run with every sample set. This standard contains the deuterated
compounds from the extraction spike mix spiked into solvent at the
concentration expected to be found in the final sample after
extraction. Once run on the instrument, this allows the data
processor to know what 100% recovery from the extract should have
been, and allows slight variations in concentration from the
theoretical for the extraction spike mix to be taken into account.
The responses from the sample versus the recovery standard are used
to calculate the efficiency.
[0211] The internal standard quantitation method is a robust method
that accounts for variations in both the extraction process and in
the instrument runs. The internal standards are spiked into both
the analyte curve and the extractions at the same amount. This
allows a response ratio to be calculated. The ratio is the response
of the analyte divided by the response of the internal standard.
The curve that is generated is then concentration (x-axis) versus
response factor (y-axis). Since a relative response is measured,
changes in instrument ionization conditions or extraction
efficiencies should not affect the quantitation. For example, if
the ratio of analyte to internal standard in a sample is one, and
half the sample is spilled, the ratio will still be one, and the
correct concentration value will be calculated based on the
curve.
[0212] The extracted cigarette smoke condensate samples are
submitted to the mass spectrometry facility where they are
aliquotted into labeled vials to be run. There are also several
instrument checks that are preformed in order to make sure the
GC/MS system is operating properly. Before samples are run, an
automatic instrument tune is performed to make sure the mass axis
and peak widths are properly calibrated, and to make sure the
instrument electronics are within acceptable ranges. The vacuum is
checked to make sure there are no leaks. Once the samples are ready
to run, a "primer" sample is run first to stabilize the instrument
response. Then a solvent blank containing the solvent used to
prepare the samples is injected to make sure there is no
contamination in the solvent or the instrument. The midpoint of the
curve is then run to make sure the instrument response has not
shifted significantly from when the curve was run. The 100%
recovery sample is injected next, followed by the samples. After
each batch of samples is run, the 100% recovery standard is
injected again, in order to compensate for any changes in the
instrument over time.
[0213] Chemstation automatically quantitates the raw data after the
instrument run is completed. A qualified mass spectrometrist then
reviews the data to check for any interferents, contaminants, and
to check the overall quality of the data. This data is then
transferred into MS Excel where data manipulation, including
conversion from pg/.mu.L to ng/cigarette, and statistics are
performed.
[0214] Levels of key PAHs from Kentucky Reference cigarettes
(KRC-1R3F) are provided in ng/cigarette in Table 7a and in ng/mg
CSC in Table 7b, as measured using GC/MS as described above. Levels
of key PAHs from Kentucky Reference cigarettes (KRC-1R4F) are
provided in ng/cigarette in Table 8a and in ng/mg CSC in Table
8b.
TABLE-US-00007 TABLE 7a PAHs in Kentucky Reference Cigarettes
(ng/cigarette) KRC-1R3F-101601-01 KRC-1R3F-101501-01
KRC-1R3F-101701-01 ng/cigarette ng/cigarette ng/cigarette Average
Key Compounds (average of 3 runs) (average of 2 runs) (average of 3
runs) (n = 8) Stdev % CV phenanthrene 88.32 84.32 81.54 84.72 3.41
4.02 2-methylanthracene 46.83 44.21 44.84 45.30 1.36 3.01 pyrene
25.97 24.89 24.71 25.19 0.68 2.71 chrysene 12.42 11.72 12.31 12.15
0.38 3.11 benzo[a]pyrene 6.68 6.45 6 49 6.54 0.12 1.86
TABLE-US-00008 TABLE 7b PAHs in Kentucky Reference Cigarettes
(ng/mg CSC) KRC-1R3F-101601-01 KRC-1R3F-101601-01
KRC-1R3F-101601-01 ng/mg CSC ng/mg CSC ng/mg CSC Key Compounds
(average of 3 runs) (average of 2 runs) (average of 3 runs) Average
Stdev % CV phenanthrene 6.04 5.95 5.85 5.95 0.09 1.59
2-methylanthracene 3.20 3.12 3.22 3.18 0.05 1.66 pyrene 1.78 1.76
1.77 1.77 0.01 0.61 chrysene 0.85 0.83 0.88 0.85 0.03 3.31
benzo[a]pyrene 0.46 0.46 I 0.47 0.46 0.01 1.19
TABLE-US-00009 TABLE 8a PAHs in Kentucky Reference Cigarettes
(ng/cigarette) KRC-1 R4F-101501-01 KRC-1 R4F-101601-01 KRC-1
R41---101401-01 KRC-1 R4F-101701-03 ng/cigarette ng/cigarette
ng/cigarette ng/cigarette Average % Key Compounds (average of 2
runs) (average of 3 runs) (average of 4 runs) (average of 3 runs)
(n = 12) Stdev CV phenanthrene 58.02 56.74 63.43 57.92 59.03 2.99
5.07 2-methylanthracene 33.55 33.35 33.43 35.63 33.99 1.09 3.22
pyrene 17.63 17.61 18.62 18.15 18.00 0.48 2.68 chrysene 8.57 8.28
8.70 8.85 8.60 0.24 2.80 benzo[a]pyrene 5.48 5.49 5.62 5.60 5.54
0.07 1.30
TABLE-US-00010 TABLE 8b PAHs in Kentucky Reference Cigarettes
(ng/mg CSC) KRC-1 R4F-101501-01 KRC-1 R4F-101601-01 KRC-1
R41---101401-01 KRC-1 R4F-101701-03 ng/mg CSC ng/mg CSC ng/mg CSC
ng/mg CSC Average % Key Compounds (average of 2 runs) (average of 3
runs) (average of 4 runs) (average of 3 runs) (n = 12) Stdev CV
phenanthrene 6.44 6.58 7.33 6.57 6.73 0.40 5.99 2-methylanthracene
3.72 3.87 3.86 4.04 3.87 0.13 3.34 pyrene 1.96 2.04 2.15 2.06 2.05
0.08 3.90 chrysene 0.95 0.96 1.00 1.00 0.98 0.03 2.84
benzo[a]pyrene 0.61 0.64 0.65 0.64 0.63 0.02 2.76
Effect of Charcoal Filter on PAHs
[0215] A study was conducted to determine the most effective type
of carbon to utilize in carbon filled filters for cigarettes,
particularly 100% filled cavity filters. Carbon filled cavity
filters have been used by a number of tobacco companies in the
United States and abroad to help remove gasses and volatiles from
cigarette smoke. FIG. 1 illustrates the effectiveness of a 100%
filled cavity in removing a host of organics and HCN from cigarette
smoke. Despite this, to date, no United States company has used a
100% filled charcoal filter. However, the carbon's effectiveness in
removing neutral non-polar molecules, such as PAHs, from the
mainstream gasses has not been investigated, nor has the potential
of a more active form of carbon been studied.
[0216] King size cigarettes with a Baumgartner 100% filled charcoal
cavity were prepared. The charcoal cavity was opened and the carbon
removed. This cavity was then refilled with the different Calgon
carbon samples, as listed in Table 9. For each carbon sample, 120
cigarettes were prepared, which allowed for analysis to be done in
triplicate. Each of these samples was smoked using the FTC
protocol. After smoking, the CSC was extracted from the Cambridge
pads using the Extraction Protocol described above and samples were
submitted for mass spectroscopy analysis for PAHs. The results of
the analysis are provided in Table 9 and FIG. 3.
TABLE-US-00011 TABLE 9 PAHs for Various Charcoal Types (Fresh)
2-methyl benzo[b/k] benzo[a] FIL. EXP. phenanthrene anthracene
pyrene chrysene fluoranthrene pyrene tar Baumgartner 133.73 53.70
33.89 15.40 15.78 9.91 9.87 100% SULFUSORB 12 99.89 48.36 27.24
13.58 13.87 8.68 9.83 CENTAUR 499 101.71 50.22 27.54 13.47 15.24
9.52 9.12 SORBITE DI 110.20 55.16 29.15 14.08 15.77 9.84 9.40 PMTC
113.83 45.45 30.31 12.69 10.91 7.11 10.3 3267-79-03 127.55 45.96
31.04 13.22 11.45 7.54 9.63 SORBITE HA 89.31 36.92 24.47 10.62 8.93
5.93 9.83
[0217] In addition, four more samples were prepared approximately
one month later for most of the carbon samples, as well as a new
sample, SCCW 14x40. For each of these samples, 120 cigarettes were
prepared, as described above, and each sample was then smoked
according to the FTC protocol. The results of the analysis are
provided in Table 10.
TABLE-US-00012 TABLE 10 PAHs for Various Charcoal Types (After
Exposure to Atmosphere for 1 Month) 2-methyl benzo[b/k] benzo[a]
FIL. EXP. phenanthrene anthracene pyrene chrysene fluoranthene
pyrene tar CA filter 155.32 45.76 33.22 14.21 6.65 5.54 14.05
Baumgartner 105.45 32.41 25.31 10.51 6.47 4.83 10.72 SULFUSORB 12
111.10 33.49 26.03 11.07 6.26 4.46 10.76 PMTC 93.92 30.99 24.71
10.43 6.28 4.84 10.95 SORBITE HA 114.19 32.36 26.39 11.00 6.64 4.45
10.20 SCCW 14 .times. 40 117.53 32.79 25.58 10.67 6.46 4.30
10.32
[0218] Seven different charcoal types were studies to determine
their potential effectiveness in removing PAHs, primarily
benzo[a]pyrene, from cigarette smoke. As is seen in Table 9 and
when compared to the commercially available carbon 100% filled
carbon filter from Baumgartner, four of the Calgon carbon samples
(Sulfusorb, PMTC, Sorbite HA, and 3267-79-03) were very effective
in reducing all of the PAH levels. The other two carbons (Centaur
and Sorbite DI) were effective for reducing some of the PAHs, but
neither gave a significant reduction in the benzo[a]pyrene
level.
[0219] These results suggest that Calgon Sorbite HA is a superior
adsorbent than conventional activated charcoal for removing certain
PAHs. To confirm the results, certain samples were retested. A
different GC-MS quantitative method was used to obtain the results
in Table 10 than was used to obtain the results in Table 9. The new
method, used to obtain the results in Table 10, resulted in a
decrease in all the PAH levels across the board, which can be seen
by comparing the Baumgartner data in Table 9 and Table 10. These
two samples should result in the same PAH levels, but Table 10 is
significantly lower. Despite this change, it is possible to
determine whether the experimental carbons are more effective than
the commercially available one, by comparing them to a new
Baumgartner sample analyzed with the new GC-MS method.
[0220] Table 10 shows that the PAH levels for all of the samples,
including the commercially available Baumgartner filter, are
statistically the same. It is believed that the experimental
charcoals lost their increased activity over time and are no more
effective than the industry standards charcoals after extended
exposure to atmospheric conditions. When the first experiments were
conducted, the experimental charcoal had just arrived from Calgon
and was sealed in airtight containers. These containers were opened
and the cigarette samples were prepared and smoked within a one
week time frame. During the month between the first and second set
of experiments, the charcoals were stored in their shipping
containers, which were no longer airtight.
[0221] It can therefore be concluded that the use of any charcoal
that considerably reduces PAH levels, especially benzo[a]pyrene,
over that of conventional activated charcoal is only worthwhile if
the production process, from production of the filter to delivery
of the cigarette to consumer, is completed under a week. Any longer
time frame and the added benefits of the new charcoal are lost.
Thus, it is generally satisfactory to use the standard commercially
available charcoal filter. However, if activated charcoals are
available that retain their activity beyond that of the charcoals
investigated, then it may be advantageous to use such charcoals.
Alternatively, different adsorbent materials may be added to the
filter cavity besides charcoal or in addition to charcoal, which
may result in lowering the PAH levels below those observed for
conventional activated charcoal.
Reduction in Carbazole Levels
[0222] Experiments were conducted to compare the levels of
carbazole in smoke from cigarettes containing tobacco incorporating
palladium particles and magnesium nitrate to those of comparable
cigarettes not containing the catalyst system. Carbazole is used as
a surrogate for azaarene compounds, which are potent carcinogens. A
catalyst system was prepared as described in the first Example, and
applied to third blend of tobacco. The quantification for carbazole
in the cigarette smoke condensate showed that the carbazole is
reduced over 29% when the catalyst system is used, as shown in
Table 11.
TABLE-US-00013 TABLE 11 Commercial Blend (Not Filtered) Carbazoles
In HRC Carbazoles In PG REFERENCE EXPERIMENTAL Reduced 379.89
ng/cig.sup.a HRC060101 266.21 ng/cig.sup.a PG-21-070-01 29.92%
386.03 ng/cig HRC060501 -- -- .sup.adata obtained with no recovery
corrected
Reduction in NitroPAHs Levels
[0223] Exposure of PAHs to NO.sub.2 and nitric acid impurity in
NO.sub.2 may result in degradation of PAHs and formation of
nitroarenes (or nitroPAHs) with increased mutagenicity. The
suggested NO.sub.3 radical-initiated reaction mechanism is as
follows.
##STR00002##
[0224] The catalyst system described in the examples above
incorporates magnesium nitrate, which may lead to the formation of
nitroarenes or nitroPAHs as described above. Five nitroarenes,
which have been categorized as Reasonably Anticipated to be Human
Carcinogens on the 9th Report on Carcinogens Revised January 2001
by U.S. Department of Health and Human Services, were selected as
indicators, although other nitroarenes such as nitronaphthalene,
nitromethylnaphthalene and nitroacenaphthene might have higher
yields. These nitroarenes include 1-nitropyrene, 4-nitropyrene,
6-nitrochrysene, 1,6-dinitropyrene and 1,8-dinitropyrene.
[0225] HPLC-FL (High Performance Liquid
Chromatography-Fluorescence) was used as separation and detection
equipment. A double endcapped XDB Zobax Eclipse C18 column (46
mm.times.150 mm, 3.5 .mu.m) was used. Mobile phase consisted of two
solvent systems, A and B. A was 100% Acetonitrile and B was a 25 mM
Na.sub.2HPO.sub.4 aqueous solution. The mobile phase gradient was
50% A+50% B for the first 5 minutes and 40% A+60% B for the
remaining 9 minutes. Fluorescence detection used E.sub.x=360,
E.sub.m=430 for 1-nitropyrene, 4-nitropyrene and 6-nitrochrysene
and E.sub.x=369, E.sub.m=442 for 1,6-dinitropyrene and
1,8-dinitropyrene.
[0226] Nitroarenes on pad (90 mm diameter Cambridge glass fiber)
were extracted by 40 ml.times.2 acetone, 15 min.times.2 shaking at
150 rmp. After evaporating the solvent at 30.degree. C. to dryness,
the extracts were brought up into methylene chloride 1 ml.times.5.
The methylene chloride solution was then driven through a 1.5 g SCX
cartridge conditioned with at least 10 ml methylene chloride at a
natural flow rate. The sample flask was rinsed with 1 ml.times.5
methylene chloride and the rinse was used to rinse the loaded SCX
cartridges also. All solution coming off the cartridge was
collected. The cartridge was sucked dry. The collected solution was
evaporated down to dryness. The residue was brought up to 2 ml by
methylene chloride. Then, 10 mg zinc dust, 20 .mu.l acetic acid and
20 .mu.l water had been added into the solution and the reaction
proceeded for 30 min. The reaction mixture was filtered by a 1 cm
long, 0.55 cm diameter silica gel column. The clear solution thus
obtained was then driven through a 500 mg SCX cartridge
(preconditioned with 3 ml methylene chloride), again at natural
flow rate. After loading, the cartridge was sucked dry again before
eluting the cartridge with 6 ml of 30% TEA (tetra-ethyl-amine)
methanol solution. The elutes were collected in a 10 ml volumetric
flask and then diluted with methanol to 10 ml for HPLC-FL
detection.
[0227] HPLC-FL was selected as the separation and detection system,
because nitroarenes are generally not thermally stable in a GC
injection system and a fluorescence detector has low detection
limit (1-10 pg in air matrix). However, nitroarenes do not have a
fluorescence emission. Therefore, in order to be able to be
detected by fluorescence detector, nitroarenes have to be reduced
to corresponding aminoarenes that have strong fluorescence
emissions. Aminoarenes are basic. Their basicity depends greatly
upon the amino groups they have on their parent rings. Usually, the
more amino groups the compound has, the stronger its basicity.
Among the five compounds selected as described above,
1,6-diaminopyrene and 1,8-diaminopyrene have stronger basicity than
1-aminopyrene, 4-aminopyrene and 6-aminochrysene. To avoid the peak
broadening, coeluting, and tilting effect caused by the binding of
the basic compounds with the weak acidic OH groups on silica
substrates of the HPLC C18 separation column, the double endcapped
C18 column and 25 mM Na.sub.2HPO.sub.4 aqueous mobile phase were
applied. FIG. 4 shows the spectrum of all five standards we
separated under our developed HPLC-FL condition. Table 12 presents
the parameters of five peaks in FIG. 4. The standard curve, which
is linear, had been set up afterwards for quantification.
TABLE-US-00014 TABLE 12 Peak Parameters of Standards Standards
T.sub.rt W.sub.h/2 F.sub.T N 1,6-diaminopyrene 3.576 0.117 1.139
5207 1,8-diaminopyrene 4.254 0.119 1.126 7102 4-aminopyrene 9.478
0.132 1.114 28355 1-aminopyrene 10.123 0.139 1.074 29554
6-aminochrysene 12.426 0.176 1.057 27492 T.sub.rt: Retention time;
W.sub.h/2: Peak width at half height; F.sub.r: USP tailing factor;
N: Efficiency; For a good shape peak, tailing factor of 1, high
efficiency, and narrow peak width are preferred.
[0228] The extraction of nitroarenes included two steps. The first
step was to extract the nitroarenes into solution. The second step
was to reduce the nitroarenes into corresponding aminoarenes so
that they can be detected. Each step had its own clean-up stage to
reduce the interference as much as possible.
[0229] In order to ensure that the designed extraction, reduction
and clean-up procedures are working, experiments with standards
were carried out. Results indicated that SCX (strong cation
exchange, propylsulfonic acid) cartridges can not only get rid of
interfering aromatic amine in the first clean-up step, but can also
separate target analytes from other interferences in the second
clean-up step, since standards were held tight on the cartridge.
Different bases at different concentrations were investigated for
their capability to elute the on-hold standards off the cartridge
with high recovery. Ammonium hydroxide methanol solution, sodium
hydroxide ethanol solution, sodium hydroxide aqueous solution and
tetraethylamine (TEA) methanol solution were all investigated. The
30% TEA methanol solution was observed to give superior results,
namely, a 80%-90% recovery.
[0230] Reduction of nitroarenes to corresponding aminoarenes was
shown to give the best recovery, 83%-85%, when glacial acetic acid
was selected from amongst different concentrations of glacial,
hydrochloric, and formic acids investigated for use in combination
with zinc dust. However, the same amount of water as of acetic acid
was added such that so that no amide, a side compound that
decreases the recovery, was produced.
[0231] The extraction of standards spiked onto cigarette smoke
condensate from Kentucky Reference cigarettes (KRC-1R4F CSC matrix)
exhibits 63.4%-71.3% recoveries.
[0232] The extraction, detection, and quantification methods was
demonstrated to provide satisfactory results with standards of all
five target analytes. The methods may be used to determine whether
nitroarenes are produced in cigarette smoke condensates.
Reduction in Catechol and Phenol Levels
[0233] Experiments were conducted to compare the levels of catechol
and phenol in smoke from cigarettes containing tobacco
incorporating palladium particles and magnesium nitrate to those of
comparable cigarettes not containing the catalyst system. A
catalyst system was prepared as described in the first Example, and
applied to similar blends to those used above. The tobacco
containing the catalyst system was fashioned into cigarettes.
Comparable cigarettes were fashioned from tobacco without the
catalyst system. As the data in Tables 13-16 demonstrate,
substantial reductions in both phenol and catechol levels were
observed in cigarettes containing the catalyst system. The FTC
smoking protocol and the Massachusetts protocol, both well known in
the art, were used in this experiment
TABLE-US-00015 TABLE 13 Control Cigarettes - FTC Method CSC/cig. 5
cigs./pad CSC wt. (g) (mg) Area Con. (ng/.mu.l) Con. (ng/.mu.l)
Con. (.mu.g/cig) Average STDEV % CV KRC-072501-01 catechol 0.048
9.6 120.42 4.953 2.477 49.53 44.123 4.831 10.95 phenol 31.721 0.618
0.309 6.180 6.030 0.210 3.483 KRC-072501-02 catechol 0.047 9.4
103.90 4.261 2.131 42.61 phenol 31.432 0.612 0.306 6.120
KRC-072501-03 catechol 0.045 9.0 98.207 4.023 2.012 40.23 phenol
29.656 0.579 0.290 5.790 catechol y = 23.88275x + 2.13633 (inj. 10
.mu.l) phenol y = 52.59205x - 0.773268 (inj. 10 .mu.l)
TABLE-US-00016 TABLE 14 Control Cigarettes - Mass. Method CSC/cig.
Con. Con. Con. 2 cigs./pad CSC wt. (g) (mg) Area (ng/.mu.l)
(ng/.mu.l) (.mu.g/cig) Average STDEV % CV KRC-080701-04 Injection 1
catechol 0.044 22 187.68 8.084 2.021 101.05 100.01 1.476 1.476
phenol 62.036 1.255 0.314 15.688 15.538 0.212 1.365 Injection 2
catechol 0.044 22 183.8 7.917 1.979 98.963 phenol 60.801 1.231
0.308 15.388 KRC-080701-05 Injection 1 catechol 0.046 23 187.68
8.084 2.021 101.05 100.71 0.486 0.483 phenol 60.186 1.218 0.305
15.225 15.200 0.035 0.233 Injection 2 catechol 0.046 23 186.39
8.029 2.007 100.36 phenol 59.977 1.214 0.304 15.175 KRC-080701-06
Injection 1 catechol 0.045 22.5 176.51 7.602 1.901 95.025 95.075
0.071 0.074 phenol 51.878 1.052 0.263 13.150 13.144 0.009 0.067
Injection 2 catechol 0.045 22.5 176.69 7.61 1.903 95.125 phenol
51.861 1.051 0.263 13.138 catechol y = 23.15112x + 0.518686 (inj.
10 .mu.l) phenol y = 49.88311x - 0.585298 (inj. 10 .mu.l)
TABLE-US-00017 TABLE 15 Cigarettes with Catalyst System - FTC
Method CSC/cig. Con. Con. Con. 5 cigs./pad CSC wt. (g) (mg) Area
(ng/.mu.l) (ng/.mu.l) (.mu.g/cig) Average STDEV % CV % reduction
PG-19-059-10 catechol 0.074 14.8 135.84 5.845 2.923 58.450 58.377
0.683 1.170 28.53 phenol 74.325 1.502 0.751 15.020 14.757 0.6559
4.445 47.50 PG-19-059-11 catechol 0.069 13.8 133.99 5.766 2.883
57.660 phenol 69.293 1.401 0.701 14.010 PG-19-059-12 catechol 0.067
13.4 137.16 5.902 2.951 59.020 phenol 75.418 1.524 0.762 15.240
PG-19-054-10 catechol 0.053 10.6 103.23 4.437 2.219 44.370 41.723
2.322 5.565 phenol 38.967 0.793 0.397 7.930 7.747 0.163 2.099
PG-19-054-11 catechol 0.046 9.2 93.20 4.003 2.002 40.030 phenol
37.769 0.769 0.385 7.690 PG-19-054-12 catechol 0.055 11 94.901
4.077 2.039 40.770 phenol 37.419 0.762 0.381 7.620
TABLE-US-00018 TABLE 16 Cigarettes with Catalyst System - Mass.
Method CSC/cig. Con. Con. Con. 2 cigs./pad CSC wt. (g) (mg) Area
(ng/.mu.l) (ng/.mu.l) (.mu.g/cig) Average STDEV % CV % reduction
PG-19-059-01 catechol 0.068 34 255.62 11.019 5.510 137.738 134.588
9.189 6.828 25.71 phenol 73.246 1.48 0.740 18.500 16.533 1.729
10.460 43.01 PG-19-059-02 catechol 0.06 30 230.62 9.939 4.970
124.238 phenol 60.278 1.220 0.610 15.250 PG-19-059-03 catechol
0.074 37 263.12 11.343 5.672 141.788 phenol 62.654 1.268 0.634
15.850 PG-19-054-01 catechol 0.042 21 369.37 15.932 3.983 99.575
99.985 2.151 2.152 phenol 75.446 1.524 0.381 9.525 9.423 0.591
6.272 PG-19-054-11 catechol 0.043 21.5 363.78 15.691 3.923 98.069
phenol 78.882 1.593 0.398 9.956 PG-19-054-03 catechol 0.045 22.5
379.5 16.37 4.093 102.313 phenol 69.566 1.406 0.352 8.788 catechol
y = 23.15112x + 0.518686 (inj. 10 .mu.l) phenol y = 49.88311x -
0.585298 (inj. 10 .mu.l)
Determination of Phenolic Compounds
[0234] Phenolic compounds in mainstream (MS) smoke have been
detected with the use of High Performance Liquid Chromatography
(HPLC). The method utilizes certain features of published methods,
including: Risner et al., "A High Performance Liquid
Chromatographic Determination of Major Phenolic Compounds in
Tobacco Smoke" Journal of Chromatographic Science, Vol. May 1990,
239; and Adams et al., "Carcinogenic agents in cigarette smoke and
the influence of nitrate on their formation" Carcinogenesis, Vol. 5
no. 2 194, 221, the contents of which are incorporated herein by
reference in their entireties.
[0235] Mainstream smoke obtained using standard smoking methods was
collected on a glass fiber filter pad. After smoking, the filter
pad was extracted and analyzed for phenolic compounds. The HPLC
method used selective fluorescence detection for the determination
of hydroquinone, resorcinol, catechol, phenol, o-cresol, m-cresol,
and p-cresol. The seven phenolic compounds were separated by
gradient elution. The peaks of m-cresol and p-cresol overlapped,
and were therefore not able to be separated.
[0236] In order to separate the phenolic compounds, a gradient
elution system was used. This system ensured that the seven
compounds were separated for proper quantification. The elution
system is documented in Table 17. Suitable A and B solutions
include 100% Acetonitrile a 25 mM Na.sub.2HPO.sub.4 aqueous
solution, respectively, however in certain embodiments other
solutions may be preferred.
TABLE-US-00019 TABLE 17 Gradient Profile for Separation Time (min)
% A % B Flow (ml/min) 0 95 5 1 30 70 30 1 35 70 30 1 40 0 100 1 45
95 5 1 50 95 5 1
[0237] A selective florescence profile was created for the
quantification of the phenolic compounds. Each analyte has a
specific excitation and emission wavelength. The Florescence
detector used the selective florescence profile listed in Table
18.
TABLE-US-00020 TABLE 18 Selective Florescence Profile Time (min)
Excitation (nm) Emission (nm) 0 304 338 8 284 313 11 280 325 16 274
298 25 285 310
[0238] FIG. 5 illustrates is a typical chromatogram generated from
the HPLC instrument. The peaks, from left to right, correspond to
hydroquinone, resourcinol, catechol, phenol, and o-cresol. Each
peak, once separated, generates an area corresponding to the
luminescence (LU). The area is then converted into a concentration
in ng/.mu.L. By implementing a shorter column, run time could be
reduced by about 35% or more, and solvent usage could be
reduced.
Reduction of Volatile Gases
[0239] The effect of the palladium catalyst system on volatile
gases, such as NO, HCN and CH.sub.3CN, during the smoking process
was investigated. Two production cigarettes were prepared, a
baseline cigarette (no catalyst) and a production cigarette
(containing the catalyst, similar to the OMNI Full Flavor King
Size), to determine what kind of effect the catalyst system had on
volatiles. A leading competitor's full flavor and light cigarettes
were also tested, as well as a Kentucky Reference cigarette, IR4F,
which permitted comparison of the production cigarette's volatile
levels to the competitor's levels. These cigarettes were smoked on
a single port smoking machine provided by K. C. Automation.
Downstream from the cigarette port was incorporated a residual gas
analyzer (RGA) from MKS Instruments. The RGA is a self-contained
mass spectrometer configured to analyze the mainstream smoke every
0.5 seconds for NO, HCN, and CH.sub.3CN.
[0240] Analyzing the volatile gases produced during the smoking
process is a difficult process, since it is not possible to collect
them on the Cambridge pads. It is therefore common practice to trap
volatiles in an alcohol trap, such as isopropanol, downstream from
the cigarette. Once the volatiles have been trapped in the alcohol,
it is possible, with some difficulty, to extract the volatiles
using a GC/MS and a variable temperature cryogenic cooler. To avoid
the difficulty associated with this method, a new system was
designed for analyzing volatiles in cigarette smoke. As stated
above, a RGA was attached to a single port smoking machine, which
permitted direct sampling of the mainstream smoke as well as side
stream smoke. The RGA permits analysis of the cigarette smoke while
the cigarette is smoking instead of in a different step, as in the
conventional method discussed above.
[0241] The RGA instrument is a stand-alone mass spectrometer that
is specifically set up to detect certain volatiles, including
nitric oxide, hydrogen cyanide, and acetonitrile. The RGA can,
however, be readily customized to search for any volatile with an
atomic weight below 200 amu. As the cigarette is smoked, the
mainstream gas passes through a Cambridge pad, which removes any
particulate matter, then down towards the exhaust port. The RGA's
capillary tube is attached to the exhaust port, which allows very
small aliquots of the smoke to be sampled every 0.5 seconds. This
frequent data collection makes it possible to actually see the
volatile levels increase as the cigarette is puffed, as illustrated
in FIG. 6. Once the cigarette has been smoked, the volatile data
can then be analyzed, as shown in Table 19. PG-19-081 is a baseline
Woods I blend containing no catalyst, and incorporating a cellulose
acetate filter. PG-19-090 is a Woods I blend, palladium treated
with a 30% reduction in nitrate, made with a 409 paper, and
incorporating a cellulose acetate-charcoal-cellulose acetate
filter.
TABLE-US-00021 TABLE19 Comparison of Volatiles PG-19-081 PG-19-090
Marlboro Marl. Lts. 1R4F NO 0.0248 0.0434 0.0207 0.0132 0.0180 HCN
0.0340 0.0210 0.0320 0.0174 0.0186 CH.sub.3CN 0.0209 0.0102 0.0176
0.0095 0.0132
[0242] As shown in Table 19, the baseline cigarette, PG-19-081,
compares very closely with the Marlboro full flavor in all three
volatiles studied. It should be noted that attempts were made to
study several other volatiles, including benzene, toluene, dimethyl
nitrosamine, and several nitroalkanes, but to date none of this
compounds have ever been observed using this method. When the
catalyst was present in the cigarette, as in PG-19-090, an increase
in the NO level was seen, which was due to the increased nitrate
level, but the HCN and CH.sub.3CN levels were reduced by 35.2% and
51.2%. Direct comparison of PG-19-090 to the Marlboro full flavor
showed a two-fold increase in the NO level for the full flavor
PG-19-090 cigarette. Despite this increase in NO, the full flavor
PG-19-090 cigarette had HCN and CH.sub.3CN levels significantly
lower (34.4% and 42.1% respectively) than the Marlboro full flavor,
and were much closer to the amounts found for Marlboro Lights and
1R4Fs.
[0243] The data demonstrate that in addition to reducing the PAH
levels, the catalyst system also yields a major reduction of HCN
and CH.sub.3CN concentrations. As expected, the NO concentration
was elevated due to the addition of nitrate to the catalyst system.
The higher NO concentration may make the task of producing a
pleasurable tasting cigarette more challenging. It may be possible
to reduce the nitrate level in the catalyst system without reducing
the catalyst's effectiveness in reducing PAHs, thereby reducing the
NO concentration. It may also be possible to reduce NO
concentration without making changes to the catalyst system by
changing the cigarette's construction, for example, by using a
different paper or filter. By changing the porosity of the
cigarette paper, burn rate and ventilation may be changed, which
may possibly reduce the NO concentration. Also, there are numerous
NO scavengers that may be incorporated into the filter cavity,
which may prove to be very effective in extracting NO from
mainstream smoke.
Reduction in Volatiles by Charcoal Filter
[0244] Experiments were conducted to compare the levels of
reduction of various gas phase components from cigarette smoke by
cavity filters having different fill levels. Experiments were
conducted using Baumgartner CAVIFLEX filters. With the CAVIFLEX
filter, the cavity may be filled to almost 100% of volume,
typically 5 to 95% of volume, with carbon or other types of
granules. When the cavity is filled to capacity, the smoke passes
through all of the carbon bed resulting in a highly efficient vapor
phase adsorption. To optimize and adjust the amount of vapor phase
retained by the filter, certain inert materials or inactivated
carbon can be mixed with granules of activated carbon in the
cavity. Examples of low cost granular inert material include
semolina (a milled product of durum wheat) and inert carbon.
[0245] FIG. 7 illustrates the gas phase removal efficiency of
CAVIFLEX filters containing different weights of active carbon 208C
mixed with semolina. As the weight of active carbon in the filter
increases, a corresponding increase in retention of gas phase
components is observed. Table 20 provides data concerning reduction
in levels of various volatile components by a reference cigarette,
and cigarettes equipped with CAVIFLEX filters containing 5 mg, 10
mg, 15 mg, 20 mg, 30 mg, 40 mg, and 50 mg activated carbon. FIG. 8
provides gas phase retention for dual coal filters containing 20,
40, 60, 80, and 100 mg carbon, respectively.
TABLE-US-00022 TABLE 20 CAVIFLEX Gas Phase Removal Efficiency for
Various Weights of Active Carbon Reference 5 mg % 10 mg % 15 mg %
20 mg % 30 mg % 40 mg % 50 mg % Compounds name .mu.g/cig. retention
retention retention retention retention retention retention
METHANOL 142.8 4 -13 24 16 48 40 57 ACETALDEHYDE 1374.0 18 23 34 39
55 54 70 ACROLEINE 118.1 27 35 51 55 72 73 82 FURANNE 42.8 22 34 46
50 68 69 81 PROPANAL 81.6 24 34 47 52 69 70 81 ACETONE 419.2 22 34
49 52 71 71 81 METHYL ACETATE 50.1 20 34 46 47 69 69 60 ISOPRENE
509.3 19 40 47 53 72 74 83 PENTANE 41.4 18 31 41 45 70 68 93 1-3
PENTADIENE 17.6 25 41 53 57 76 77 86 METHACROLEINE 14.6 29 45 57 64
83 87 95 ISOBUTYRALDEHYDE 23.5 25 51 51 56 75 79 90 BUTANONE-2
111.0 27 41 56 57 75 76 84 BENZENE 68.8 27 43 55 58 77 77 87 2,5
DMF 28.8 13 36 49 49 71 71 83 TOLUENE 92.2 34 51 65 63 82 82 89
ETHYL BENZENE 10.5 45 51 72 76 93 92 100 META-XYLENE 18.1 37 46 66
51 91 93 100 HYDROCYANURIC ACID 22 9 27 42 71 66 67 ACETONITRILE
173.8 57 51 66 72 87 87 86 ACRYLONITRILE 19.6 19 13 37 52 76 78 80
PROPIONITRILE 35.1 22 21 45 55 79 80 80 METHACRYLONITRILE 4.8 22 26
44 57 79 83 83 ISOBUTYRONITRILE 11.1 23 26 47 59 81 82 82 MEAN -
TOTAL 25 33 49 53 75 75 83
[0246] Table 21 provides data concerning reduction in levels of
various volatile components by a reference cigarette, and
cigarettes equipped with CAVIFLEX filters containing 4% (or 5 mg)
activated carbon--Version A, 12% (or 16 mg) activated
carbon--Version B, 20% (or 26 mg) activated carbon--Version C, 30%
(or 39 mg) activated carbon--Version D, 40% (or 52 mg) activated
carbon--Version E, 60% (or 78 mg) activated carbon--Version F.
Table 22 provides data concerning reduction in levels of various
volatile components by a reference cigarette, and cigarettes
equipped with traditional filters containing 52 mg activated
carbon--Version G. and 78 mg activated carbon--Version H. FIG. 9
illustrates the gas phase removal efficiency of the different
versions of the CAVIFLEX filters containing active carbon BR255
mixed with inert carbon (Versions A through F). Again, as the
weight of active carbon in the filter increases, a corresponding
increase in retention of gas phase components is observed. FIG. 9
includes comparison data for traditional charcoal filters (Versions
G and H). On a carbon weight per filter basis, the CAVIFLEX filter
exhibits a greater gas phase removal efficiency than the
traditional charcoal filter.
TABLE-US-00023 TABLE 21 CAVIFLEX Gas Phase Removal Efficiency for
Various Weights of Active Carbon Version A Version B Version C
Version D Version E Version F refer- 4% (5 mg) 12% (16 mg) 20% (26
mg) 30% (39 mg) 40% (52 mg) 60% (78 mg) Compounds ence .mu.g/ %
.mu.g/ % .mu.g/ % .mu.g/ % .mu.g/ % .mu.g/ % name .mu.g/cig cig
retention cig retention cig retention cig retention cig retention
cig retention METHANOL 239.2 239.0 0 210.4 12 127.5 47 110.4 54
81.2 66 55.7 77 ACETALDEHYDE 1761.7 1543.4 12 1112.9 37 870.2 51
607.1 66 526.5 70 306.8 83 ACETONITRILE 104.9 95.3 9 64.4 39 42.2
60 31.7 70 26.2 75 13.8 87 ACROLEINE 133.2 92.8 30 55.5 58 43.5 67
25.5 81 22.1 83 12.3 91 FURANNE 38.8 30.6 21 19.2 51 16.1 59 10.1
74 9.4 76 5.6 86 PROPANAL 114.8 88.8 23 57.3 50 44.8 61 27.8 76
24.1 79 14.2 88 ACETONE 304.4 246.3 19 151.7 50 109.1 64 65.0 79
54.1 82 23.2 92 METHYL- 44.6 35.4 21 23.1 48 17.5 61 0.0 100 9.6 78
5.6 87 ACETATE ISOPRENE 660.0 463.1 30 260.1 61 201.6 69 115.9 82
111.7 83 49.4 93 PENTANE 24.8 21.1 15 13.3 46 10.1 59 6.9 72 6.2 75
3.9 84 1,3 PENTADIENE 40.3 30.5 24 19.8 51 15.0 63 10.6 74 9.6 76
0.0 100 PROPIONITRILE 19.6 16.5 16 10.0 49 7.3 63 4.5 77 4.0 80 0.0
100 BUTANONE-2 78.0 63.1 19 38.5 51 27.1 65 17.5 78 14.6 81 7.6 90
CROTONAL- 21.0 15.5 26 10.2 51 8.1 61 5.4 74 5.4 74 0.0 100 DEHYDE
HEXANE 14.0 12.7 9 6.9 51 5.2 63 4.6 67 3.1 78 0.0 100 BENZENE 61.3
46.3 24 27.5 55 20.2 67 12.8 79 11.0 82 7.3 88 2,5 DMF 21.5 17.5 19
9.8 54 7.4 66 4.7 78 3.8 82 3.2 85 TOLUENE 69.8 57.0 18 33.8 52
23.5 66 15.5 78 14.3 80 8.3 88 ETHYLBENZENE 8.6 7.1 17 5.0 42 2.9
66 0.0 100 0.0 100 0.0 100 META-XYLENE 9.8 8.9 9 5.4 45 3.0 69 0.0
100 0.0 100 0.0 100 MEAN - TOTAL 18 48 62 78 80 91
TABLE-US-00024 TABLE 22 Gas Phase Removal Efficiency for
Traditional Filters Version G Version H Compounds Reference 52 mg
78 mg name .mu.g/cig .mu.g/cig % retention .mu.g/cig % retention
METHANOL 239.2 152.5 36 89.2 63 ACETALDEHYDE 1761.7 1122.2 36 522.6
70 ACETONITRILE 104.9 62.3 41 28.1 73 ACROLEINE 133.2 67.9 49 23.9
82 FURANNE 38.8 21.7 44 9.9 74 PROPANAL 114.8 64.5 44 26.4 77
ACETONE 304.4 166.9 45 59.5 80 METHYLACETATE 44.6 25.3 43 0.0 100
ISOPRENE 660.0 352.4 47 111.2 83 PENTANE 24.8 13.9 44 7.2 71 1,3
PENTADIENE 40.3 22.5 44 10.4 74 PROPIONITRILE 19.6 11.1 43 4.4 78
BUTANONE-2 78.0 43.1 45 16.8 78 CROTONALDEHYDE 21.0 12.0 43 5.3 75
HEXANE 14.0 7.9 44 4.5 68 BENZENE 61.3 34.3 44 12.2 80 2,5 DMF 21.5
11.2 48 5.2 76 TOLUENE 69.8 39.8 43 15.5 78 ETHYLBENZENE 8.6 4.9 43
0.0 100 META-XYLENE 9.8 6.0 39 0.0 100 MEAN - TOTAL 43 79
[0247] In a preferred embodiment, a cigarette containing tobacco
treated with a palladium catalyst system is equipped with a filter
incorporating a 100% carbon filled cavity. Table 23 lists various
volatile compounds present in mainstream smoke from a typical
conventional cigarette and the typical percent decrease observed in
those compounds when passed through a filter incorporating a 100%
carbon filled cavity.
TABLE-US-00025 TABLE 23 Compounds In Mainstream Smoke Removed by
100% Carbon Filled Cavity Compound Percent Decrease* Methanol 77
Acetaldehyde 83 Acroleine 87 Furanne 91 Acetone 91 Propanaal 86
Hexane 100 Methyl acetate 87 Acetone 88 Issoprene 93 Pentane 84
1,3-pentanediene 100 Methacroleine 95 Isobutyraldehyde 90
Butanone-2 90 Benzene 88 2,5-dimethylformamide 85 Toluene 89
Ethylbenzene 100 Metaxylene 100 Crotonaldehyde 100 Acetonitrile 60
Hydrogen cyanide 100 AcryInitrile 80 Propionitrile 80
Methacrylonitrile 83 Isobutyronitrile 82 *Research data from
Baumgartner
Reduction in PAH, TSNA, and Phenol Levels
[0248] Experiments were conducted to compare the levels of selected
PAHs (including phenanthrene, 2-methyl-anthracene, pyrene,
chrysene, benzo[b/k]fluoranthene, and benzo[a]pyrene), TSNAs
(including N'-nitrosonornicotine (NNN),
4-(N-nitrosomethylamino)-1-(3-pyridyl)-1-butanone (NNK),
N'-nitrosoanatabine (NAT), and N'-nitrosoanabasine (NAB)),
carbazole, catechol and phenol in smoke from cigarettes containing
tobacco incorporating palladium particles and magnesium nitrate to
those of comparable cigarettes not containing the catalyst system.
A catalyst system was prepared as described in the first Example,
and applied to a commercial tobacco blend. The tobacco containing
the catalyst system was fashioned into king sized cigarettes.
Comparable cigarettes were fashioned from tobacco without the
catalyst system. As the data in Table 24 demonstrates, substantial
reductions in the levels of PAHs, carbazole, catechol, and phenol
were observed in both mainstream and sidestream smoke from
cigarettes containing the catalyst system. Reductions in the level
of 4-(N-nitrosomethylamino)-1-(3-pyridyl)-1-butanone (NNK) were
observed.
TABLE-US-00026 TABLE 24 Carcinogen Levels in Cigarettes with and
Without Catalyst System PAHs (ng/cig) benzo CSC 2-methyl- [b/k]
Cigarette Code Type (mg) phenanthrene anthracene pyrene chrysene
fluoranthrene BaP carbazole FF-KS, Reg. PG- main 12.1 83.03 28.48
23.20 12.39 5.52 4.49 325.00 Catalyst, 19- 2.5 2.96 4.14 1.74 6.90
2.37 2.45 3.86 CA-C-CA 100% 082 14.2% 46.54 37.77 30.16 12.84 17.04
19.05 No Change (AP200), 917 side 29.11 1805.44 401.50 277.94
225.42 60.36 42.28 -- paper 0.84 6.08 6.93 7.95 4.19 5.80 4.31 --
-- No No Change No No No No -- Change Change Change Change Change
FF-KS, Reg. PG- main 12.92 79.03 27.75 22.82 11.81 5.79 4.65 --
Catalyst, 19- 1.29 1.38 1.54 2.14 2.65 0.70 1.52 -- CA-C-CA 100%
086 8.1% 49.12 39.37 31.31 16.88 12.90 16.11 -- (AP200), 409 paper
LT-KS, Reg. PG- main 9.64 64.60 22.95 18.40 9.57 4.42 3.77 --
Catalyst, 19- 0.60 1.46 0.81 0.68 1.02 1.61 3.22 -- CA-C-CA 70% 084
31.0% 58.41 49.84 44.62 32.67 33.50 31.97 -- (AP300), 917 paper
ULT-KS, Reg. PG- main 6.51 52.14 19.00 15.20 8.19 3.87 3.24 --
Catalyst, C 19- 2.12 1.87 5.52 1.22 3.37 4.80 1.36 -- impreg-nated
085 53.7% 66.43 58.48 54.24 42.40 41.80 41.48 -- CA (laser air
diluted, AP300), 409 paper FF-KS, Catalyst PG- main 12.68 83.34
27.86 23.55 12.40 5.80 4.57 305.85 (30% redu in 19- 0.86 2.26 2.80
2.81 3.36 1.18 0.19 1.22 NO3), 087 9.8% 46.34 39.12 29.10 12.76
12.79 17.49 No Change CA-C-CA 100% (AP200), 917 side 28.22 1689.40
382.08 257.91 207.82 57.98 40.05 -- paper 0.68 4.70 6.22 4.44 8.95
3.93 3.44 -- -- No No Change No No No No -- Change Change Change
Change Change Baseline: No PG- main 14.05 155.32 45.76 33.22 14.21
6.65 5.54 316.23 Catalyst, CA 19- 3.55 10.05 1.61 1.42 3.85 5.37
1.89 4.59 filter, 409 paper 081 -- -- -- -- -- -- -- -- TSNAs
Phenols CSC (ng/cig) (.mu.g/cig) Cigarette Code Type (mg) NNN NAT
NAB NNK Catechol Phenol FF-KS, Reg. PG- main 12.1 70 20 200 50
53.58 8.653 value Catalyst, 19- 2.5 -- -- -- -- -- -- % CV CA-C-CA
100% 082 14.2% -- -- -- -- 18.23 43.764 % dec. (AP200), 917 side
29.11 -- -- -- -- -- -- value paper 0.84 -- -- -- -- -- -- % CV --
-- -- -- -- -- -- % dec. FF-KS, Reg. PG- main 12.92 -- -- -- -- --
-- value Catalyst, 19- 1.29 -- -- -- -- -- -- % CV CA-C-CA 100% 086
8.1% -- -- -- -- -- -- % dec. (AP200), 409 paper LT-KS, Reg. PG-
main 9.64 -- -- -- -- -- -- value Catalyst, 19- 0.60 -- -- -- -- --
-- % CV CA-C-CA 70% 084 31.0% -- -- -- -- -- -- % dec. (AP300), 917
paper ULT-KS, Reg. PG- main 6.51 -- -- -- -- -- -- value Catalyst,
C 19- 2.12 -- -- -- -- -- -- % CV impreg-nated 085 53.7% -- -- --
-- -- -- % dec. CA (laser air diluted, AP300), 409 paper FF-KS,
Catalyst PG- main 12.68 53.64 9.283 value (30% redu in 19- 0.86 %
CV NO3), 087 9.8% -25% -27% -24% No 18.14 39.67 % dec. CA-C-CA 100%
Change (AP200), 917 side 28.22 -- -- -- -- -- -- value paper 0.68
-- -- -- -- -- -- % CV -- -- -- -- -- -- -- % dec. Baseline: No PG-
main 14.05 -- -- -- 90 65.53 15.39 value Catalyst, CA 19- 3.55 --
-- -- -- -- -- % CV filter, 409 paper 081 -- -- -- -- -- -- -- %
dec.
[0249] Experiments were conducted to compare the level of the
tobacco specific nitrosamine NNK in the sidestream smoke of an Omni
cigarette containing a palladium catalyst system and a commercially
available Marlboro cigarette. The catalyst system produced a
reduction of about 25% in the level of NNK in sidestream smoke over
the baseline value. The level of NNK in the sidestream smoke of the
Omni cigarette was measured at 900 ng/cigarette compared to 1,200
ng/cigarette in the sidestream smoke of the Marlboro cigarette. The
data suggest that the catalyst system of preferred embodiments may
substantially reduce the levels of certain carcinogens in
sidestream smoke, thereby reducing the level of exposure to such
carcinogens of individuals exposed to secondhand smoke from
cigarettes employing the catalyst system.
[0250] Experiments were conducted to compare the levels of various
compounds in a cigarette incorporating a palladium catalyst system
(identified by the BIO designation in the sample code), a Kentucky
Reference cigarette (identified by the KRC designation in the
sample code), and a Marlboro cigarette (identified by the MRC
designation in the sample code. Results of these experiments are
provided in Tables 25-43. Unless otherwise specified, the
measurements were obtained for mainstream smoke.
[0251] Tables 25 and 26 provide a comparison of catechol, phenol
and tar levels in the three cigarettes. The cigarette including a
palladium catalyst system displayed a substantial reduction in
catechol, phenol and tar levels over both the Kentucky Reference
and Marlboro cigarettes. Table 27 provides cigarette smoke
condensate levels for the cigarette containing the catalyst system.
Tables 28, 29, and 30 provide TSNA levels for the cigarette
containing the catalyst system. Table 31 provides cigarette smoke
condensate levels for the Marlboro cigarette. Tables 32, 33, and 34
provide TSNA levels for the cigarette containing the catalyst
system. Table 33 provides additional cigarette smoke condensate
levels for the cigarette containing the catalyst system. Tables 36
and 37 provide PAH levels for the cigarette containing the catalyst
system. Table 38 provides additional cigarette smoke condensate
levels for the Marlboro cigarette. Tables 39 and 40 provide PAH
levels for the Marlboro cigarette. Table 41 provides cigarette
smoke condensate levels in sidestream smoke for the cigarette
containing the catalyst system. Tables 42 and 43 provides PAH
levels in sidestream smoke for the cigarette containing the
catalyst system.
TABLE-US-00027 TABLE 25 Comparison of Catechol and Phenol Levels
AVG AVG CSC CATECHOL PHENOL CIG CSC (MG) UG UG/ UG UG/ WGT # OF CSC
WGT (MG) PER PER STAN % CSC PER STAN % CSC SAMPLE (G) CIG PUFF (G)
PER CIG CIG CIG DEV CV (MG) CIG DEV CV (MG) BIO-54-020 1 1.0093 10
5.44 0.107 10.7 10.5 46.079 1.054 2.29 4.38852 5.267 0.3 5.69 0.502
2 0.9838 10 5.28 0.105 10.5 3 1.0039 10 5.305 0.103 10.3 KRC-101801
1 1.004 10 6.5 0.146 14.6 15.133 72.81 2.171 2.98 4.8112 14.94 0.35
2.34 0.987 2 1.017 10 6.58 0.148 14.8 3 1.0201 10 6.73 0.16 16
MRC-101801 1 0.9109 10 6.25 0.123 12.3 12.4 58.222 3.191 5.48
4.69532 10.91 0.65 5.96 0.88 2 0.9301 10 6.2 0.13 13 3 0.9263 10
6.3 0.119 11.9 KRC-101801 MRC-10180 CATECHOL REDUCTION: 36.712
20.855463 PHENOL REDUCTION: 64.737 51.715535 TAR REDUCTION: 30.617
15.322581
TABLE-US-00028 TABLE 26 Comparison of Catechol and Phenol Levels
SAM CATECHOL PHENOL CATECHOL PHENOL STD INJ INJ CONC CONC CONC CONC
VOL VOL (UG/# (UG/# 3 Methyl Int Std (NG/UL) (NG/UL) (UL) (UL) OF
CIG) OF CIG) Recov Recov 3 Methyl BIO-54-020 1 9.25315 1.01119 10
20 46.26575 5.05595 33.206 99.56 33.35 2 94.0559 1.12214 10 20
47.02795 5.6107 33.538 100.56 3 8.98894 1.02712 10 20 44.9447
5.1356 33.565 100.64 KRC-101801 1 14.06301 3.03592 10 20 70.21505
15.1796 35.125 105.32 2 14.76777 2.9072 10 20 73.83885 14.536
34.333 102.94 3 14.85493 3.0194 10 20 74.27465 15.097 34.465 103.34
MRC-101801 1 11.5452 2.10992 10 20 57.726 10.5496 34.156 102.41 2
12.32629 2.33192 10 20 61.63145 11.6596 34.711 104.07 3 11.06166
2.10364 10 20 55.3083 10.5182 34.64 103.86 FTC METHOD Sample Name
BIO-54-020 KRC-1R3F MRC-SOFT PACK Blend WOODSI Filter Type CA 100%
CA Cigarette paper 15460 Cigarette Type FF KS Additives (e.g.
catalyst) CATALYST Conditioning Time (hours) 24 24 24 Temperature
(.degree. F.) 75 74 74 Relative Humidity (%) 51 51 51
TABLE-US-00029 TABLE 27 CSC Levels of Cigarette With Catalyst
System Deg. F. % RH Smoke Room Conditions: 74.3 52 BIO-54-020-04
BIO-54-020-05 BIO-54-020-06 CSC(mg)-10 cig. 10.1 8.6 11 Puffs 5.39
5.4 5.5 Avg. Wt. (g) 1.005 1.005 1.003
TABLE-US-00030 TABLE 28 TSNA Levels of Cigarette With Catalyst
System Est. Conc. (ng/ml)/10 cigs BIO-54-020-04 BIO-54-020-05
BIO-54-020-06 Run 1 Run 2 Run 1 Run 2 Run 1 Run 2 NNN 931.5 855
789.5 831.2 879.1 853.1 NAT 855.4 779.1 751.6 802.2 793.8 772.6 NAB
159.5 129.8 134.9 142.2 139.7 138.1 NNK 388.2 337 327.3 372.7 357.6
358.6
TABLE-US-00031 TABLE 29 TSNA Levels of Cigarette With Catalyst
System Est. Conc. ng/cigarette Est. Conc. ng/cigarette
BIO-54-020-04 BIO-54-020-05 BIO-54-020-06 Avg. of 3 St Dev of % cv
of Run 1 Run 2 Avg. Run 1 Run 2 Avg. Run 1 Run 2 Avg. samples 3
samples 3 samples NNN 186 171 179 158 166 162 176 171 174 172 9
5.23 NAT 171 156 164 150 160 155 159 155 157 159 5 3.14 NAB 31.9 26
29 27 28.4 27.7 27.9 27.6 27.8 28.2 0.7 2.48 NNK 77.6 67.4 72.5
65.5 74.5 70 71.5 71.7 71.6 71 1 1.41
TABLE-US-00032 TABLE 30 TSNA Levels of Cigarette With Catalyst
System Est. Conc. ng/mg csc/cigarette Est. Conc. ng/mg
csc/cigarette BIO-54-020-04 BIO-54-020-05 BIO-54-020-06 Avg. of 3
St Dev of % cv of Run 1 Run 2 Avg. Run 1 Run 2 Avg. Run 1 Run 2
Avg. samples 3 samples 3 samples NNN 18.45 16.93 17.69 18.36 19.33
18.85 15.98 15.51 15.75 17.43 1.57 9.01 NAT 16.94 15.43 16.19
17.479 18.66 18.07 14.43 14.05 14.24 16.17 1.92 11.87 NAB 3.158
2.57 2.864 3.137 3.307 1.222 2.54 2.511 2.526 2.871 0.348 12.12 NNK
7.687 6.673 7.18 7.612 8.667 8.14 6.502 6.52 6.511 7.277 0.819
11.25
TABLE-US-00033 TABLE 31 CSC Levels of Marlboro Cigarette Deg. F. %
RH Oct. 19, 2001 Smoke Room Conditions: 74.3 52 MRC-101901-04
MRC-101901-05 MRC-101901-06 CSC (mg) 12.4 11.7 12.1 Puffs n/a 6.28
6.15 Avg. Wt. (g) 0.9126 0.918 0.917
TABLE-US-00034 TABLE 32 TSNA Levels of Marlboro Cigarette Est.
Conc. (ng/ml)/10 cig. MRC-101901-04 MRC-101901-05 MRC-101901-06 Run
1 Run 2 Run 1 Run 2 Run 1 Run 2 NNN 884.7 879.9 854.4 916.3 870.9
848.1 NAT 658.6 639.2 626.6 679.2 688.5 646.1 NAB 86.4 88.5 87.1
89.7 84.3 78.4 NNK 584.8 578 541.3 598.4 576.7 561.5
TABLE-US-00035 TABLE 33 TSNA Levels of Marlboro Cigarette Est.
Conc. ng/cigarette Est. Conc. ng/cigarette MRC-101901-04
MRC-101901-05 MRC-101901-06 Avg. of 3 St Dev of % cv of Run 1 Run 2
Avg. Run 1 Run 2 Avg. Run 1 Run 2 Avg. samples 3 samples 3 samples
NNN 177 176 177 171 183 177 174 170 172 175 3 1.71 NAT 132 128 130
125 136 131 138 129 134 132 2 1.52 NAB 17.3 17.7 17.5 17.4 17.9
17.7 16.9 15.7 16.3 17.2 0.8 4.65 NNK 117 115.6 116.3 108.3 119.7
114 115.3 112.3 113.8 115 1 0.87
TABLE-US-00036 TABLE 34 TSNA Levels of Marlboro Cigarette Est.
Conc. ng/mg csc/cigarette Est. Conc. ng/cigarette MRC-101901-04
MRC-101901-05 MRC-101901-06 Avg. of 3 St Dev of % cv of Run 1 Run 2
Avg. Run 1 Run 2 Avg. Run 1 Run 2 Avg. samples 3 samples 3 samples
NNN 14.27 14.19 14.23 14.61 15.66 15.14 14.4 14.02 14.21 14.53 0.53
3.65 NAT 10.62 10.31 10.47 10.711 11.61 11.16 11.38 10.68 11.03
10.89 0.37 3.4 NAB 1.394 1.427 1.411 1.489 1.533 1.511 1.393 1.296
1.345 1.422 0.084 5.91 NNK 9.432 9.323 9.378 9.253 10.229 9.741
9.532 9.281 9.407 9.509 0.202 2.12
TABLE-US-00037 TABLE 35 CSC Levels of Cigarette With Catalyst
System Original Tobacco/Spray Batch Cigarette Batch Extraction Code
mg of CSC # of cigarettes mg of CSC/cigarette BIO-54-020-01
BIO-54-020-01 BIO-75-005-04 452 40 11.30 BIO-54-020-02
BIO-75-005-05 461 40 11.53 BIO-54-020-03 BIO-75-005-06 452 40
11.30
TABLE-US-00038 TABLE 36 PAH Levels of Cigarette With Catalyst
System versus Marlboro Cigarette ng/cigarette, corrected for
compared to Key Compounds: % recovery Stnd. Dev. 1888 MRC-101901 %
reduction error phenanthrene 66.51 1.47 Reduction 29.92 1.59
2-methylanthracene 26.87 0.10 Reduction 35.71 0.64 pyrene 19.23
0.18 Reduction 24.88 0.86 chrysene 10.26 0.08 Reduction 23.93 1.64
benzo[b/k]fluoranthene 6.51 0.15 Reduction 4.95 0.15 benzo[a]pyrene
6.91 0.06 Reduction 7.14 0.08
TABLE-US-00039 TABLE 37 PAH Levels of Cigarette With Catalyst
System BIO-75-005- % recoveries# BIO-75-005-04 BIO-75-005-05 06
D8-acenaphthylene 69.6 70.7 80.9 D10-fluorene 76.1 77.4 87.9
D10-phenanthrene 84.1 87.0 96.5 D10-anthracene 84.6 91.5 105.5
D8-carbazole N.D. N.D. N.D. D10-fluorathene 95.5 95.5 106.8
D10-pyrene 92.1 94.0 103.7 D12-benzo(a)anthracene 117.4 120.5 133.8
D12-chrysene 99.7 103.1 112.9 D12-benzo(a)pyrene 115.8 117.4
134.0
TABLE-US-00040 TABLE 38 CSC Levels of Marlboro Cigarettes Original
mg of Tobacco/Spray Batch Cigarette Batch Extraction Code mg of CSC
# of cigarettes CSC/cigarette MRC-SOFT PACK MRC-101901-01
MRC-75-005-01 520 40 13.00 MRC-101901-02 MRC-75-005-02 509 40 12.73
MRC-101901-03 MRC-75-005-03 528 40 13.40
TABLE-US-00041 TABLE 39 PAH Levels of Marlboro Cigarette
ng/cigarette, corrected for Key Compounds: % recovery Stnd. Dev.
phenanthrene 94.90 4.59 2-methylanthracene 41.80 0.73 pyrene 25.59
0.86 chrysene 13.48 0.92 benzo[b/k]fluoranthene 6.85 0.13
benzo[a]pyrene 7.44 0.05
TABLE-US-00042 TABLE 40 PAH Levels of Marlboro Cigarette
MRC-75-005- MRC-75- % recoveries# MRC-75-005-01 02 005-03
D8-acenaphthylene 97.7 78.1 93.1 D10-fluorene 106.2 87.6 103.4
D10-phenanthrene 111.8 95.2 111.6 D10-anthracene 112.2 102.4 117.6
D8-carbazole N.D. N.D. N.D. D10-fluorathene 122.6 106.1 124.1
D10-pyrene 120.2 103.5 120.8 D12-benzo(a)anthracene 155.2 135.1
158.0 D12-chrysene 134.8 113.9 134.4 D12-benzo(a)pyrene 168.1 146.0
174.9
TABLE-US-00043 TABLE 41 CSC Levels of Cigarette with Catalyst
System - Sidestream Smoke Original Tobacco/Spray Batch Cigarette
Batch Extraction Code mg of CSC # of cigarettes mg of CSC/cigarette
BIO-54-020-01 BIO-54-020-101 BIO-40-071-01 78 3 26.00
BIO-54-020-102 BIO-40-071-02 75 3 25.00 Blank BIO-40-071-03
BIO-54-020-103 BIO-40-071-04 79 3 26.33
TABLE-US-00044 TABLE 42 PAH Levels of Cigarette with Catalyst
System - Sidestream Smoke ng/cigarette, corrected for compared to
Key Compounds: % recovery Stnd. Dev. 1135-MRC-40-023-01 % reduction
error phenanthrene 1244.11 117.25 Reduced 52.85 8.18
2-methylanthracene 321.10 18.70 Reduced 45.53 5.45 pyrene 193.01
13.25 Reduced 51.18 6.18 chrysene 164.92 6.94 Reduced 60.94 6.99
benzo[b/k]fluoranthene 59.18 4.72 Reduced 48.86 6.95 benzo[a]pyrene
50.88 0.65 Reduced 29.93 1.90
TABLE-US-00045 TABLE 43 PAH Levels of Cigarette with Catalyst
System - Sidestream Smoke BIO-40- BIO-40- BIO-40- % recoveries#
BIO-40-071-01 071-02 071-03 071-04 D8-acenaphthylene 57.5 61.8 26.1
69.6 D10-fluorene 66.3 70.9 44.1 78.9 D10-phenanthrene 77.5 83.4
67.1 90.1 D10-anthracene 74.7 80.4 41.9 87.1 D8-carbazole N.D. N.D.
N.D. N.D. D10-fluorathene 88.5 95.4 81.1 102.3 D10-pyrene 84.4 90.2
74.6 96.7 D12-benzo(a)anthracene 114.7 115.5 79.4 125.6
D12-chrysene 92.6 97.3 83.8 105.1 D12-benzo(a)pyrene 104.2 110.3
33.3 117.7
[0252] The above description provides several methods and materials
of the present invention. This invention is susceptible to
modifications in the methods and materials, such as the choice of
catalyst, smokable material, filter, and the like, as well as
alterations in the fabrication methods and equipment. Such
modifications will become apparent to those skilled in the art from
a consideration of this disclosure or practice of the invention
disclosed herein. Consequently, it is not intended that this
invention be limited to the specific embodiments disclosed herein,
but that it cover all modifications and alternatives coming within
the true scope and spirit of the invention as embodied in the
attached claims.
[0253] Every patent and other reference mentioned herein is hereby
incorporated by reference in its entirety.
* * * * *