The impact of puff frequency on respirable particulate matter in mainstream cigarette smoke.

BACKGROUND: Inhalation of particulate matter (PM) from cigarette smoke is hazardous to smokers and non-smokers. This contribution simulates the deposition of cigarette PM on the lung surface by trapping tobacco smoke particulates on Croton megalocarpus biochar. This study investigated one commercial cigarette (MM) and one local cigarette (RR). METHODOLOGY: Biochar was incorporated into the filters of MM and RR cigarettes in order to adsorb PM from mainstream cigarette smoke. A weighed 5 mg of biochar with adsorbed cigarette PM was analyzed using a scanning electron microscope and a Fourier transform infrared spectrometer. The size distribution of cigarette smoke particulates was processed using ImageJ software. RESULTS: At 15 s puff time, the mean particulate diameters for the commercial and the local cigarettes, respectively, can be classified as coarse ≈ PM10 . Conversely, the mean particulate diameter at 2 s puff time for the commercial cigarette falls under the ultrafine classification of ≤PM2.5 , whereas at the same puff time, the mean particulate diameter for the local cigarette was approximately PM2.5 . Data from Fourier transform infrared spectroscopy indicate the PM in the two model cigarettes contains aromatic structures that feature the C=C bond characterized by an intense absorption band at δs (1600 cm-1 ). CONCLUSIONS: This study found that PM in mainstream cigarette smoke depends on puff time. Although cigarette smoking was conducted for two model cigarettes, this study can be extended to any other form of cigarette. Moreover, this study emphasizes the need for comprehensive studies on real-world cigarette smoking conditions, taking into account cigarette smokers who use larger puff volumes.

A review of the characteristic properties of selected tobacco chemicals and their associated etiological risks.

OBJECTIVES: Despite the quantum of research findings on tobacco epidemic, a review on the formation characteristics of nicotine, aldehydes and phenols, and their associated etiological risks is still limited in literature. Accordingly, knowledge on the chemical properties and free radical formation during tobacco burning is an important subject towards unravelling the relationship between smoking behaviour and disease. This review investigates how scientific efforts have been advanced towards understanding the release of molecular products from the thermal degradation of tobacco, and harm reduction strategies among cigarette smokers in general. The mechanistic characteristics of nicotine and selected aldehydes are critically examined in this review. For the purpose of this work, articles published during the period 2004-2021 and archived in PubMed, Google Scholar, Medley, Cochrane, and Web of Science were used. The articles were selected based on the health impacts of cigarette smoking, tobacco burning kinetics, tobacco cessation and tobacco as a precursor for emerging diseases such as Covid-19. CONTENT: The toxicity of cigarette smoke is directly correlated with its chemical composition derived from the pyrolysis of tobacco stem and leaves. Most of the harmful toxic substances are generated by pyrolysis during smoking and depends on pyrolysis conditions. Detailed studies have been conducted on the kinetics of nicotine by use of robust theoretical models in order to determine the rate constants of reactions in nicotine and those of nicotine dissociation via C-C and C-N scission, yielding pyridinyl and methyl radicals, respectively. Research has suggested that acetaldehyde enhances the effect of nicotine, which in turn reinforces addiction characteristics whereas acrolein and crotonaldehyde are ciliatoxic, and can inhibit lung clearance. On the other hand, phenol affects liver enzymes, lungs, kidneys, and the cardiovascular system while m-cresol attacks the nervous system. SUMMARY AND OUTLOOK: The characteristics of chemical release during tobacco burning are very important in the tobacco industry and the cigarette smoking community. Understanding individual chemical formation from cigarette smoking will provide the necessary information needed to formulate sound tobacco reform policies from a chemical standpoint. Nonetheless, intense research is needed in this field in order to prescribe possible measures to deter cigarette smoking addiction and ameliorate the grave miseries bedevilling the tobacco smoking community.

A review of tobacco abuse and its epidemiological consequences.

Aim: The economic burden caused by death and disease in the world is credited mainly to tobacco use-currently linked to approximately 8,000,000 deaths per year with approximately 80% of these faralities reported in low and middle income economies. The World Health Organization (WHO) estimates that nearly 7,000,000 deaths are attributed to direct tobacco use, while approximately 1,200,000 non-smokers exposed to second hand cigarette smoke die every year. Accordingly, tobacco use is a major threat to the public health infrastructure; therefore, proper cessation interventions must be put in place to curb tobacco abuse and ease economic and social burdens caused by the tobacco epidemic. Methods: A systematic review was conducted to investigate how scientific efforts have been advanced towards harm reduction among smokers and non-smokers. Relevant articles published during the period 2010-2020 in PubMed, Crossref, Google scholar, and Web of Science were used in this study. The articles were selected based on health impacts of cigarette smoking, tobacco cessation and emerging diseases, including Covid-19. Various cessation strategies have been identified although their efficiency is yet to match the desired results. Results: A series of carcinogenic chemicals are generated during cigarette smoking resulting in serious health complications such as cancer and mutagenesis. The precursors for tobacco induced diseases are toxic and carcinogenic chemicals of the nitrosamine type, aldehydes, polonium-210 and benzo[a]pyrene, which bio-accumulate in the body system during cigarette smoking to cause disease. Rehabilitation facilities, use of drugs to diminish the desire to smoke, heavy taxation of tobacco products and warning labels on cigarettes are some of the cessation strategies employed towards curbing tobacco abuse. Conclusion: The need for further research to develop better methods and research based policies for safe cigarette smoking and workable cessation strategies must be a priority in order to deal with the tobacco epidemic. Campaigns to promote tobacco cessation and abstinence are recommended in this review as a sure measure to mitigate against the deleterious impacts caused by cigarette smoking and tobacco abuse.

Dioxin and dibenzofuran like molecular analogues from the pyrolysis of biomass materials-the emerging challenge in bio-oil production.

INTRODUCTION: The aggressive search for renewable energy resources and essential pyrosynthetic compounds has marked an exponential rise in the thermal degradation of biomass materials. Consequently, clean and sustainable transport fuels are increasingly desirable in a highly industrialized economy, for energy security and environmental protection. For this reason, biomass materials have been identified as promising alternatives to fossil fuels despite the challenges resulting from the possible formation of toxic nitrogen-based molecules during biomass degradation. In order to understand the free radical characteristic challenges facing the use of bio-oil, a brief review of the effects of free radicals in bio-oil is presented. METHODOLOGY: Pyrolysis was conducted in a tubular flow quartz reactor at a residence time of 2 s at 1 atm. pressure, for a total pyrolysis time of 5 min. The thermal degradation of biomass components was investigated over the temperature range of 200 to 700 °C typically in 50 °C increments under two reaction conditions; pyrolysis in N2 and oxidative pyrolysis in 5% O2 in N2. The pyrolysate effluent was analysed using a Gas chromatograph hyphenated to a mass selective detector (MSD). RESULTS: The yield of levoglucosan in the pyrolysis of cellulose in the entire pyrolysis temperature range was 68.2 wt % under inert conditions and 28.8 wt % under oxidative conditions. On the other hand, formaldehyde from pyrolysis of cellulose yielded 4 wt % while that from oxidative pyrolysis was 7 wt % translating to ⁓ 1.8 times higher than the yield from pyrolysis. Accordingly, we present for the first time dioxin-like and dibenzofuran-like nitrogenated analogues from an equimassic pyrolysis of cellulose and tyrosine. Levoglucosan and formaldehyde were completely inhibited during the equimassic pyrolysis of cellulose and tyrosine. CONCLUSION: Clearly, any small amounts of N-biomass components such as amino acids in cellulosic biomass materials can inhibit the formation of levoglucosan-a major constituent of bio-oil. Overall, a judicious balance between the production of bio-oil and side products resulting from amino acids present in plant matter should be taken into account to minimize economic losses and mitigate against negative public health concerns.

Mechanistic formation of hazardous molecular heterocyclic amines from high temperature pyrolysis of model biomass materials: cellulose and tyrosine.

BACKGROUND: Research inventories on the co-pyrolysis of major biomass components such as cellulose with amino acid materials is scarce in literature despite the fact that such studies are critical in understanding toxic product relations from high temperature cooking, combustion of bio-fuels, cigarette smoking and forest fires. This paper explores, quantitatively, the yields of heterocyclic nitrogenated molecular reaction products of grave mutagenetic concern from the co-pyrolysis of model biomass materials; tyrosine and cellulose. Research has established that heterocyclic amines such as isocyanates are mutagens as well precursors for asthma, and other respiratory disorders. METHODS: An equimassic mixture of tyrosine and cellulose (50 ± 2 mg) by weight were pyrolyzed in a tubular quartz reactor in flowing nitrogen at 1 atm. Besides, varying combinations of tyrosine and cellulose in the ratios 3:1 and 1:3 were also explored for comparison. The reaction time was set at 2 s so as to simulate combustions events in nature. The pyrolysate was collected over 5 mL dichloromethane and characterized using a gas chromatograph coupled to a mass spectrometer detector. RESULTS: Evidently, it was noted that 1-methylindazole was released in high yields at 300 °C, constituting ~ 300 µg in the entire pyrolysis temperature range (200-700 °C). Nonetheless, isoindazole gave the highest yield ~ 730 µg while 1-naphthyl isocyanate gave a total yield of ~ 336 µg in the same temperature range. Remarkably, the change in char yield between 300 and 450 °C for the pyrolysis of 25% tyrosine in 75% cellulose was found to be ~ 48% whereas the change in char yield for the pyrolysis of 75% tyrosine in 25% cellulose was 49%. CONCLUSION: The char and tar yields considered important residues of biomass burning have been reported in this study and found to be consistent with other research output in literature. The striking similarities of % yield of char across all temperatures for various combinations was the most significant observation in this investigation-char yield was independent of the mixing ratio during pyrolysis. From a mechanistic standpoint, it was noted that tyrosine inhibited cellulose based nitrogenated products. Thus N-products dominated the O-products.

Free radicals and ultrafine particulate emissions from the co-pyrolysis of Croton megalocarpus biodiesel and fossil diesel.

BACKGROUND: The atmosphere has become a major transport corridor for free radicals and particulate matter from combustion events. The motivation behind this study was to determine the nature of particulate emissions and surface bound radicals formed during the thermal degradation of diesel blends in order to assess the health and environmental hazards of binary transport fuels. METHODOLOGY: Accordingly, this contribution explored the interactions that occur when Croton megalocarpus biodiesel and fossil diesel in the ratio of 1:1 by weight were co-pyrolyzed in a quartz reactor at a residence time of 0.5 s under an inert flow of nitrogen at 600 °C. The surface morphology of the thermal char formed were imaged using a Feld emission gun scanning electron microscope (FEG SEM) while Electron paramagnetic resonance spectrometer (EPR) was used to explore the presence of free radicals on the surface of thermal char. Molecular functional groups adsorbed on the surface of thermal char were explored using Fourier transform infrared spectroscopy (FTIR). RESULTS: FTIR spectrum showed that the major functional groups on the surface of the char were basically aromatic and some methylene groups. The particulate emissions detected in this work were ultrafine (~ 32 nm). The particulates are consistent with the SEM images observed in this study. Electron paramagnetic resonance results gave a g-value of 2.0027 characteristic of carbon-based radicals of aromatic nature. Spectral peak-to-peak width (∆Hp-p) obtained was narrow (4.42 G). CONCLUSIONS: The free radicals identified as carbon-based are medically notorious and may be transported by various sizes of particulate matter on to the surface of the human lung which may trigger cancer and pulmonary diseases. The nanoparticulates determined in this work can precipitate severe biological health problems among humans and other natural ecosystems.

The Degradation of O-ethyltoluene and 1,3,5-Trimethylbenzene in Lake Naivasha Wetland, Kenya.

The primary degradation of benzene derivatives in aquatic environments occurs via microbial and chemical processes. This study investigated the kinetic degradation of o-ethyltoluene and 1,3,5-trimethylbenzene in the wetland of Lake Naivasha. Sediment samples were collected from 6:00 AM to 6:00 PM at intervals of 3 h during the dry season of December 2017. The sediment samples were air dried, ground into powder, followed by soxhlet extraction in a binary mixture of methanol and hexane in the ratio of 1:1. The extract was analyzed using gas chromatograph with mass selective detector. Variation in the concentrations of o-ethyltoluene and 1,3,5-trimethylbenzene with time was monitored kinetically. Accordingly, the half-lives for the degradation of o-ethyltoluene and 1,3,5-trimethylbenzene were 4.9 and 5.4 h, respectively, and their corresponding decay rate constants were 3.93 × 10-5 and 3.56 × 10-5 S-1. 1,3,5-Trimethylbenzene was the most persistent contaminants in the wetland.

Environmentally persistent free radicals and particulate emissions from the thermal degradation of Croton megalocarpus biodiesel.

Pyrolysis of biodiesel at high temperatures may result in the formation of transient and stable free radicals immobilized on particulate emissions. Consequently, free radicals adsorbed on particulates are believed to be precursors for health-related illnesses such as cancer, cardiac arrest, and oxidative stress. This study explores the nature of free radicals and particulate emissions generated when Croton megalocarpus biodiesel is pyrolyzed at 600 °C in an inert environment of flowing nitrogen at a residence time of 0.5 s at 1 atm. The surface morphology of thermal emissions were imaged using a field emission gun scanning electron microscope (FEG SEM) while the radical characteristics were investigated using an electron paramagnetic resonance spectrometer (EPR). A g-value of 2.0024 associated with a narrow ∆Hp-p of 3.65 G was determined. The decay rate constant for the radicals was low (1.86 × 10-8 s-1) while the half-life was long ≈ 431 days. The observed EPR characterization of Croton megalocarpus thermal particulates revealed the existence of free radicals typical of those found in coal. The low g-value and low decay rate constant suggests that the free radicals in particulates are possibly carbon-centered. The mechanistic channel for the formation of croton char from model biodiesel component (9-dodecenoic acid, methyl ester) has been proposed in this study.

Phenols from pyrolysis and co-pyrolysis of tobacco biomass components.

Phenol and its derivatives (phenol, o-, m-, p-cresols, catechol, hydroquinone, methoxy substituted phenols, etc. referred to as phenolic compounds or phenols) are well-known toxicants that exist in the environment and affect both human and natural ecosystems. This study explores quantitatively the yields of phenolic compounds from the thermal degradation (pyrolysis and oxidative pyrolysis) of common tobacco biomass components (lignin, tyrosine, ethyl cellulose, sodium alginate, and laminarin) as well as some mixtures (lignin/tyrosine, ethyl cellulose/tyrosine and sodium alginate/tyrosine) considered important in high temperature cooking, tobacco smoking, and forest fires. Special attention has been given to binary mixtures including those containing tyrosine-pyrolysis of binary mixtures of tyrosine with lignin and ethyl cellulose results in significant reductions in the yields of majority phenols relative to those from the thermal degradation of tyrosine. These results imply that the significant reductions of phenol yields in mixtures are not only dependent upon the mass fractions of the components but also the synergetic inhibition effect of biomass components on the thermal degradation of tyrosine. A mechanistic description of this phenomenon is suggested. The results may also be implied in tobacco industry that the cigarette paper (as ethyl cellulose derivative) may play a critical role in reducing the concentration of phenolic compounds released during tobacco burning.

Molecular products from the thermal degradation of glutamic acid.

The thermal behavior of glutamic acid was investigated in N2 and 4% O2 in N2 under flow reactor conditions at a constant residence time of 0.2 s, within a total pyrolysis time of 3 min at 1 atm. The identification of the main pyrolysis products has been reported. Accordingly, the principal products for pyrolysis in order of decreasing abundance were succinimide, pyrrole, acetonitrile, and 2-pyrrolidone. For oxidative pyrolysis, the main products were succinimide, propiolactone, ethanol, and hydrogen cyanide. Whereas benzene, toluene, and a few low molecular weight hydrocarbons (propene, propane, 1-butene, and 2-butene) were detected during pyrolysis, no polycyclic aromatic hydrocarbons (PAHs) were detected. Oxidative pyrolysis yielded low molecular weight hydrocarbon products in trace amounts. The mechanistic channels describing the formation of the major product succinimide have been explored. The detection of succinimide (major product) and maleimide (minor product) from the thermal decomposition of glutamic acid has been reported for the first time in this study. Toxicological implications of some reaction products (HCN, acetonitrile, and acyrolnitrile), which are believed to form during heat treatment of food, tobacco burning, and drug processing, have been discussed in relation to the thermal degradation of glutamic acid.

Molecular products from the pyrolysis and oxidative pyrolysis of tyrosine.

The thermal degradation of tyrosine at a residence time of 0.2s was conducted in a tubular flow reactor in flowing N2 and 4% O2 in N2 for a total pyrolysis time of 3min. The fractional pyrolysis technique, in which the same sample was heated continuously at each pyrolysis temperature, was applied. Thermal decomposition of tyrosine between 350 and 550°C yielded predominantly phenolic compounds (phenol, p-cresol, and p-tyramine), while decomposition between 550 and 800°C yielded hydrocarbons such as benzene, toluene, and ethyl benzene as the major reaction products. For the first time, the identification of p-tyramine, a precursor for the on of formation of p-tyramine and its degradation to phenol and p-cresol, and toxicological discussion of some of the harmful reaction products is also presented.