Martin Graham Duke

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.

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 comparative assessment of cigarette smoke aerosols using an in vitro air–liquid interface cytotoxicity test

Abstract This study describes the evaluation of a modified air-liquid interface BALB/c 3T3 cytotoxicity method for the assessment of smoke aerosols in vitro. The functionality and applicability of this modified protocol was assessed by comparing the cytotoxicity profiles from eight different cigarettes. Three reference cigarettes, 1R5F, 3R4F and CORESTA Monitor 7 were used to put the data into perspective and five bespoke experimental products were manufactured, ensuring a balanced and controlled study. Manufactured cigarettes were matched for key variables such as nicotine delivery, puff number, pressure drop, ventilation, carbon monoxide, nicotine free dry particulate matter and blend, but significantly modified for vapor phase delivery, via the addition of two different types and quantities of adsorptive carbon. Specifically manufacturing products ensures comparisons can be made in a consistent manner and allows the research to ask targeted questions, without confounding product variables. The results demonstrate vapor-phase associated cytotoxic effects and clear differences between the products tested and their cytotoxic profiles. This study has further characterized the in vitro vapor phase biological response relationship and confirmed that the biological response is directly proportional to the amount of available vapor phase toxicants in cigarette smoke, when using a Vitrocell® VC 10 exposure system. This study further supports and strengthens the use of aerosol based exposure options for the appropriate analysis of cigarette smoke induced responses in vitro and may be especially beneficial when comparing aerosols generated from alternative tobacco aerosol products.