Christopher Proctor

Reduction of aldehydes and hydrogen cyanide yields in mainstream cigarette smoke using an amine functionalised ion exchange resin

BackgroundCigarette smoking is a well recognized cause of diseases such as lung cancer, chronic obstructive pulmonary disease and cardiovascular disease. Of the more than 5000 identified species in cigarette smoke, at least 150 have toxicological activity. For example, formaldehyde and acetaldehyde have been assigned as Group 1 and Group 2B carcinogens by IARC, and hydrogen cyanide has been identified as a respiratory and cardiovascular toxicant. Active carbon has been shown to be an effective material for the physical adsorption of many of the smoke volatile species. However, physical adsorption of acetaldehyde, formaldehyde and also hydrogen cyanide from smoke is less effective using carbon. Alternative methods for the removal of these species from cigarette smoke are therefore of interest. A macroporous, polystyrene based ion-exchange resin (Diaion®CR20) with surface amine group functionality has been investigated for its ability to react with aldehydes and HCN in an aerosol stream, and thus selectively reduce the yields of these compounds (in particular formaldehyde) in mainstream cigarette smoke.ResultsResin surface chemistry was characterized using vapour sorption, XPS, TOF-SIMS and 15N NMR. Diaion®CR20 was found to have structural characteristics indicating weak physisorption properties, but sufficient surface functionalities to selectively remove aldehydes and HCN from cigarette smoke. Using 60 mg of Diaion®CR20 in a cigarette cavity filter gave reductions in smoke formaldehyde greater than 50% (estimated to be equivalent to >80% of the formaldehyde present in the smoke vapour phase) independent of a range of flow rates. Substantial removal of HCN (>80%) and acetaldehyde (>60%) was also observed. The performance of Diaion®CR20 was found to be consistent over a test period of 6 months. The overall adsorption for the majority of smoke compounds measured appeared to follow a pseudo-first order approximation to second order kinetics.ConclusionsThis study has shown that Diaion®CR20 is a highly selective and efficient adsorbent for formaldehyde, acetaldehyde and HCN in cigarette smoke. The reductions for these compounds were greater than those achieved using an active carbon. The results also demonstrate that chemisorption can be an effective mechanism for the removal of certain vapour phase toxicants from cigarette smoke.

Determination of Nicotine Absorption from Multiple Tobacco Products and Nicotine Gum

Introduction: Snus is a smokeless tobacco product traditionally used in Scandinavia and available in pouched or loose forms. The objective of this study was to determine nicotine absorption for current pouched and loose snus products in comparison with a cigarette and an over-the-counter nicotine gum. Methods: We conducted an open-label, randomized, 6-way, crossover study involving 20 healthy snus and cigarette users. One of 6 products (2 pouched snus, 2 weights of loose snus, a cigarette, and a nicotine gum) was administered at each of 6 visits. Blood samples were taken at intervals over 120 min and sensory perception assessed by questionnaire. Results: For the 4 smokeless tobacco products and the nicotine gum, blood plasma levels of nicotine were ranked according to total nicotine content as follows: loose snus (27.1 mg nicotine) > pouched snus (14.7 mg nicotine) > loose snus (10.8 mg nicotine) = pouched snus (10.7 mg nicotine) > nicotine gum (4.2 mg nicotine). The area under the plasma concentration–time curve (AUC) and maximum plasma concentration (Cmax) of nicotine ranged from 26.9 to 13.1 ng.h/ml and 17.9 to 9.1 ng.h/ml, respectively across all the products. Nicotine was absorbed more rapidly from the cigarette but systemic exposure was within the range of the smokeless tobacco products (AUC = 14.8 ng.h/ml; Cmax = 12.8 ng.h/ml). Conclusions: This study has generated new information on comparative nicotine absorption from a cigarette, loose snus, and pouched snus typical of products sold in Scandinavia. The similar nicotine absorption for 1 g portions of loose and pouched snus with approximately 11 mg of nicotine indicate that absorption kinetics were dependent on quantity of tobacco by weight and total nicotine content rather than product form.

The use of a novel tobacco treatment process to reduce toxicant yields in cigarette smoke

The US Institute of Medicine has encouraged the pursuit and development of potential reduced-exposure products (PREPs) - tobacco products that substantially reduce exposure to one or more tobacco toxicants and can reasonably be expected to reduce the risk of one or more specific diseases or other adverse health effects. One potential approach is to reduce levels of some smoke toxicant precursors, such as proteins and polyphenols, in tobacco. We describe a treatment process involving aqueous tobacco extraction and treatment with protease; filtration of the extract to remove peptides, amino acids and polyphenols, and recombination of extract and treated tobacco. The process reduced levels of protein nitrogen (59%), polyphenols (33-78%) and nicotine (12%) while sugars increased 16%. ISO mainstream smoke yields of 43 toxicants were measured from cigarettes containing treated tobaccos; lower yields of tar, nicotine, carbon monoxide (16-20%), acrylonitrile, ammonia, aromatic amines, pyridine, quinolene and hydrogen cyanide (33-51%), tobacco specific nitrosamines (25-32%); phenolics (24-56%), benzene (16%), toluene (25%) and cadmium (34%) were obtained. There were significantly increased yields of formaldehyde (49%) and isoprene (17%). Reductions in sidestream yields of nitrogenous smoke toxicants and increases in sidestream yields of several carbonyls, benzo(a)pyrene and isoprene were also observed.

Use of Classical Adsorption Theory to Understand the Dynamic Filtration of Volatile Toxicants in Cigarette Smoke by Active Carbons

The ability of two very different active carbons, a polymer-derived carbon (with ultramicropores and supermicropores, and a large volume of “transport” pores) and a coconut shell-derived carbon (predominantly ultramicroporous), to reduce the levels of volatile toxicants in cigarette smoke has been measured and compared. The polymer-derived carbon was found to be approximately twice as effective in removing the majority of measured smoke vapour-phase toxicants compared to the coconut shell-derived carbon in three different cigarette formats and with two different smoking regimes. Single-component dynamic breakthrough experiments were conducted with benzene, acrylonitrile and 2-butanone at 298 K for beds of each carbon under dry (0% RH) and wet (60% RH) conditions. Longer breakthrough times were found with the polymer-derived carbon, and breakthrough times recorded under wet conditions were found to be up to 20% shorter than those obtained under dry conditions. Correlations between micropore volume, dynamic adsorption volume and filter bed breakthrough time have been demonstrated.

An experimental method to study emissions from heated tobacco between 100-200°C

BackgroundCigarette smoke emissions are mainly produced by distillation, pyrolysis and combustion reactions when the tobacco is burnt. Some studies have shown that heating tobacco to temperatures below pyrolysis and combustion temperatures has the potential to reduce or eliminate some toxicants found in cigarette smoke. In this study, we designed a bench-top tube furnace that heats tobacco between 100-200°C and systematically studied the effects of heating temperatures on selected gas phase and aerosol phase compounds using an ISO machine-smoking protocol.ResultsAmong a list of target chemical compounds, seven toxicants (nicotine, carbon monoxide, acetaldehyde, crotonaldehyde, formaldehyde, NNN and NNK) were quantifiable but not at all temperatures examined. The levels of the compounds generally displayed an increasing trend with increasing temperatures. The observed carbon monoxide and aldehydes represented the initial thermal breakdown products from the tobacco constituents. Water was the largest measured component in the total aerosol phase collected and appeared to be mainly released by evaporation; nicotine release characteristics were consistent with bond breaking and evaporation. Quantifiable levels of NNK and NNN were thought to be the result of evaporative transfer from the tobacco blend.ConclusionsThese results demonstrate the practical utility of this tool to study low-temperature toxicant formation and emission from heated tobacco. Between 100 to 200°C, nicotine and some cigarette smoke compounds were released as a result of evaporative transfer or initial thermal decomposition from the tobacco blend.

A comparison of methods of assessing exposure to environmental tobacco smoke in non-smoking British women

Abstract Fifty-two non-smoking British women were recruited to wear personal monitors for nicotine and volatile organic compounds over a 24-h period in the autumn of 1989. The subjects also supplied samples of saliva for cotinine analysis, and answered questions regarding lifestyle and exposure to environmental tobacco smoke (ETS). The research indicates that exposure to ETS in free-living subjects is very low (mean nicotine exposure 2.3 μg m 3 ). Moreover, the greatest influence on exposure was living with a smoker, contact with smokers at work; leisure or travel having a minor impact. Salivary cotinine levels were found in subjects observed not to be exposed to ETS, hence somewhat questioning the validity of this measure for very low levels of exposure. Both of the objective measures of ETS exposure, nicotine and salivary cotinine levels, only correlated modestly with subjective assessments of exposure obtained by questionnaire.

Design and chemical evaluation of reduced machine-yield cigarettes

Experimental cigarettes (ECs) were made by combining technological applications that individually reduce the machine measured yields of specific toxicants or groups of toxicants in mainstream smoke (MS). Two tobacco blends, featuring a tobacco substitute sheet or a tobacco blend treatment, were combined with filters containing an amine functionalised resin (CR20L) and/or a polymer-derived, high activity carbon adsorbent to generate three ECs with the potential for generating lower smoke toxicant yields than conventional cigarettes. MS yields of smoke constituents were determined under 4 different smoking machine conditions. Health Canada Intense (HCI) machine smoking conditions gave the highest MS yields for nicotine-free dry particulate matter and for most smoke constituents measured. Toxicant yields from the ECs were compared with those from two commercial comparator cigarettes, three scientific control cigarettes measured contemporaneously and with published data on 120 commercial cigarettes. The ECs were found to generate some of the lowest machine yields of toxicants from cigarettes for which published HCI smoke chemistry data are available; these comparisons therefore confirm that ECs with reduced MS machine toxicant yields compared to commercial cigarettes can be produced. The results encourage further work examining human exposure to toxicants from these cigarettes, including human biomarker studies.

MEASUREMENTS OF ENVIRONMENTAL TOBACCO SMOKE IN AN AIR-CONDITIONED OFFICE BUILDING

Abstract This paper reports levels of nicotine, respirable participates, carbon monoxide, carbon dioxide and volatile organic compounds measured in the air of smokers’ and non‐smokers’ offices in a modern air‐conditioned building. The results show very low levels of environmental tobacco smoke constituents, such as nicotine, present in smokers’ offices. Moreover, the data show that smoking has little influence on the levels of volatile organic compounds found in the office air.

Approaches for the design of reduced toxicant emission cigarettes

Cigarette smoking causes serious diseases through frequent and prolonged exposure to toxicants. Technologies are being developed to reduce smokers’ toxicant exposure, including filter adsorbents, tobacco treatments and substitutes. This study examined the effect of modifications to filter ventilation, variations in cigarette circumference and active charcoal filter length and loading, as well as combinations of these features in a reduced-toxicant prototype (RTP) cigarette, on the yields of toxicants in cigarette smoke. An air-dilution mechanism, called split-tipping, was developed in which a band of porous paper in the centre of the filter tipping functions to minimise the loss of effective filter ventilation that occurs at the high flow rates encountered during human-smoking, and to facilitate the diffusional loss of volatile toxicants. As compared with conventional filter ventilation cigarettes, split-tipping reduced tar and volatile smoke constituent emissions under high flow rate machine-smoking conditions, most notably for products with a 1-mg ISO tar yield. Furthermore, mouth level exposure (MLE) to tar and nicotine was reduced among smokers of 1-mg ISO tar cigarettes in comparison to smokers of cigarettes with traditional filter ventilation. For higher ISO tar level cigarettes, however, there were no significant reductions in MLE. Smaller cigarette circumferences reduced sidestream toxicant yields and modified the balance of mainstream smoke chemistry with reduced levels of aromatic amines and benzo[a]pyrene but increased yields of formaldehyde. Smaller circumference cigarettes also had lower mainstream yields of volatile toxicants. Longer cigarette filters containing increased levels of high-activity carbon (HAC) showed reduced machine-smoking yields of volatile toxicants: with up to 97% removal for some volatile toxicants at higher HAC loadings. Split-tipping was combined with optimal filter length and cigarette circumference in an RTP cigarette that gave significantly lower mainstream (up to ~90%) and sidestream (predominately 20%–60%) smoke yields of numerous toxicants as compared with a commercial comparator cigarette under machine-smoking conditions. Significantly lower mainstream and sidestream smoke toxicant yields were observed for an RTP cigarette comprising several toxicant reducing technologies; these observations warrant further evaluation in clinical studies where real-world relevance can be tested using biomarkers of exposure and physiological effect.

Assessment of tobacco heating product THP1.0. Part 2: Product design, operation and thermophysical characterisation

ABSTRACT A novel tobacco heating product, THP1.0, that heats tobacco below 245 °C is described. It was designed to eliminate tobacco combustion, while heating tobacco to release nicotine, tobacco volatiles and glycerol to form its aerosol. The stewardship assessment approach behind the THP 1.0 design was based on established toxicological principles. Thermophysical studies were conducted to examine the extent of tobacco thermal conversion during operation. Thermogravimetric analysis of the tobacco material revealed the major thermal behaviour in air and nitrogen up to 900 °C. This, combined with the heating temperature profiling of the heater and tobacco rod, verified that the tobacco was not subject to combustion. The levels of tobacco combustion markers (CO, CO2, NO and NOx) in the aerosol of THP1.0 were significantly lower than the levels if there were any significant pyrolysis or combustion. Quantification of other tobacco thermal decomposition and evaporative transfer markers showed that these levels were, on average, reduced by more than 90% in THP1.0 aerosol as compared with cigarette smoke. The physical integrity of the tobacco consumable rod showed no ashing. Taken together, these data establish that the aerosol generated by THP1.0 is produced mainly by evaporation and distillation, and not by combustion or pyrolysis. HighlightsDesign and operation of THP1.0 tobacco heating product is described.A 5‐step thermophysical and thermochemical assessment is conducted on THP1.0.THP1.0 forms its aerosol predominantly through evaporation and distillation.Tobacco in THP1.0 is not subject to combustion.