Determination of Nicotine-Related Alkaloids in Tobacco and Cigarette Smoke by GC-FID

A simple and accurate method, gas chromatography (GC) with flame-ionization detection (FID) has been used for determination of the four main nicotine-related alkaloids in tobacco. Tobacco samples were treated with a small quantity of aqueous ammonia solution, to loosen the tobacco tissue and to convert all alkaloids to free bases, then extracted with 1:3 CH₃OH-CH₂Cl₂. A method for further simultaneous and comprehensive determination of six nicotine-related alkaloids in cigarette smoke was also developed. Because of the complexity of the cigarette smoke matrix and the small amounts of alkaloids, except nicotine, in cigarette smoke, the smoke extract was concentrated after removal of the acidic and neutral fractions. To reduce the adsorption and thermal degradation of alkaloids in the liner, especially for nornicotine, a suitable injector temperature was selected and pulsed injection mode was studied. Different cigarette smokes and tobaccos were analyzed for levels of nicotine-related alkaloids.Revised: 3 January and 21 March 2005     

卷烟主流烟气中相关成分含量的快速检测方法

建立了一种快速测定卷烟主流烟气中相关成分的方法,其中包括一氧化碳、4-(甲基亚硝氨基)-3-吡啶-1-丁酮(NNK)、苯酚、巴豆醛、氨和氰化氢6种相关成分.采用在吸烟机上同时使用溶剂捕集和滤片捕集的方式,溶剂捕集氨、氰化氢和巴豆醛,滤片捕集NNK、氨、氰化氢和苯酚,样品采集后分别在高效液相色谱、离子色谱和液相色谱/质谱...     

Determination of thiocyanate as a biomarker of tobacco smoke constituents in selected biological materials of human origin

In order to protect human health, it is necessary to biomonitor toxic substances originating from tobacco smoke in biological materials sampled from persons with different exposures to tobacco smoke constituents. Thiocyanate anion is a biomarker of exposure to tobacco smoke components which is characterized by a relatively long half‐life in the human body, i.e. 6 days. In this work, we present the results of thiocyanate determinations performed on samples of placenta, meconium, saliva, breast milk, sweat and blood. The placenta samples were subjected to accelerated solvent extraction with water. The thiocyanate concentrations were determined using ion chromatography. The analyzed biological materials were compared with regard to their applicability for biomonitoring toxic substances originating from tobacco smoke. The highest mean concentrations of thiocyanate were observed in the samples of biological materials collected from active smokers.     

Characterization of Indian cigarette tobacco and its smoke aerosol by nuclear and allied techniques

Forty brands of tobacco used in Indian cigarettes, 20 brands of bidis (tobacco rolled in wrapper leaves), 15 brands of chewing tobacco and 15 brands of snuff tobacco were analyzed by nuclear and allied techniques. The elements measured into tobacco can be grouped into seven categories from less than 1 ppm to 5% by weight. Concentration level varied from 0.5-5% for (Ca, K, Cl), 400-1500 ppm (Fe), 200-600 ppm (Na), 100-300 ppm (Ti, Mn, Br and Sr), 10-100 ppm (Cu, Zn and Rb), 1-10 ppm (Cr, Ni, Pb and La) and less than 1 ppm (As, Co, Cd, Sb, Hg and Eu). Among the above elements Cr, Ni, As, Cd, Pb, Hg and Sb are considered toxic. The percentage transfer of the elements from cigarette tobacco to smoke particles during smoking was also estimated using a smoking machine and collecting the smoke particles on a filter paper. The results show that Br, Cr, Sb and Zn have high percentage transfer from tobacco to its smoke of the order of 2-15%. Out of these Sb has the highest 15%. Cobalt, Fe and Sc have lowest percentage of transfer of the order of less than 1%. The percent transfer of these elements from tobacco to tobacco smoke is higher in case of bidis (1.5-3.0 times) as compared to cigarettes. In cigarettes also non-filter cigarettes have higher transfer (2-3 times) as compared to filter tip cigarettes.     

Magnetic solid‐phase extraction of tobacco‐specific N‐nitrosamines using magnetic graphene composite as sorbent

Tobacco‐specific N‐nitrosamines are carcinogenic components in mainstream cigarette smoke. To explore tobacco‐specific N‐nitrosamine release levels in cigarettes, a magnetic solid‐phase extraction procedure using magnetic graphene composite as sorbent for fast enrichment of tobacco‐specific N‐nitrosamine was developed. Under optimal conditions, a tobacco‐specific N‐nitrosamine determination method was successfully proposed by combining magnetic solid‐phase extraction procedure and high‐performance liquid chromatography coupled with tandem mass spectrometry. The method's limit of detection for tobacco‐specific N‐nitrosamines in mainstream cigarette smoke ranged from 0.018 to 0.057 ng/cigarette. Good linearities were obtained with correlation coefficients above 0.9992. The accuracies of tobacco‐specific N‐nitrosamines in a spiked mainstream cigarette smoke sample were from 89.3 to 109.4%, with a relative standard deviation of less than 11.2%. The proposed method has the merits of rapidity and high sensitivity. Finally, the method was successfully applied to tobacco‐specific N‐nitrosamine analysis in real samples.     

Trace elements in Turkish tobacco determined by instrumental neutron activation analysis

The concentration of 20 trace elements in nine different brands of Turkish cigarette tobacco and in a brand of pipe tobacco and in tobacco ash has been determined by instrumental neutron activation analysis. The percent transference of elements into smoke has been estimated from the amounts remaining in the ash.     

基于质谱的代谢组学方法在烟草化学中的应用研究

中烟工业公司为云南烟草“十一五”时期烟草工业科技的发展做出了指导方针,数字烟草作为实施云南烟草品牌差异化发展的六个重点领域之一,有极大的发展空间。烟草的数字性不能仅仅停留在企业的IT设备上,应该成为一种企业思维,形成企业的一种大局面观,这是数字烟草内涵的表现。烟     

沸石在去除卷烟烟气中亚硝胺的应用

吸烟污染;沸石;添加剂;沸石在去除卷烟烟气中亚硝胺的应用     

Investigation,by single photon ionisation (SPI)–time-of-flight mass spectrometry (TOFMS), of the effect of different cigarette-lighting devices on the chemical composition of the first cigarette puff

Soft single-photon ionisation (SPI)–time-of-flight mass spectrometry (TOFMS) has been used to investigate the effect of different cigarette-lighting devices on the chemical composition of the mainstream smoke from the first cigarette puff. Lighting devices examined were a Borgwaldt electric lighter, a propane/butane gas lighter, a match, a candle, and the burning zone of another cigarette. To eliminate the effects of the different masses of tobacco burnt by use of the different lighting methods a normalisation procedure was performed which enabled investigation of changes in the chemical patterns of the resulting smoke. When another cigarette was used as the lighting device, elevated levels of ammonia and other nitrogen-containing substances were observed. These are high in the sidestream smoke of the cigarette used for lighting and would be drawn into the mainstream smoke of the cigarette being lit. In contrast, smoke from the cigarette lit by the electric lighter contained slightly higher normalised amounts of isoprene. Lighting the cigarette by use of a candle resulted in larger amounts of substances, e.g. benzene, which most probably originated from thermal decomposition of wax. The composition of the first puff of smoke obtained by use of the three lighting methods with open flames (gas lighter, match, and candle) was usually similar whereas the composition of the smoke produced by use of the electric lighter and the cigarette as the lighter were more unique. The chemical patterns generated by the different lighting devices could, however, be separated by principal-component analyses. Two additional test series were also studied. In the first the cigarette was lit with an electric lighter, then extinguished, the ash was cut off, and the cigarette was re-lit. In the second the cigarette was heated in an oven to 80 °C for 5 min before being lit. These treatments did not result in changes in the chemical composition compared with cigarettes lit in the ordinary way. Figure Time-of-flight mass spectrometry (TOFMS) has been used to investigate the effect of different cigarette-lighting devices on the chemical composition of the mainstream smoke from the first cigarette puff     

Pyrolysis and combustion of tobacco in a cigarette smoking simulator under air and nitrogen atmosphere

A coupling between a cigarette smoking simulator and a time-of-flight mass spectrometer was constructed to allow investigation of tobacco smoke formation under simulated burning conditions. The cigarette smoking simulator is designed to burn a sample in close approximation to the conditions experienced by a lit cigarette. The apparatus also permits conditions outside those of normal cigarette burning to be investigated for mechanistic understanding purposes. It allows control of parameters such as smouldering and puff temperatures, as well as combustion rate and puffing volume. In this study, the system enabled examination of the effects of “smoking” a cigarette under a nitrogen atmosphere. Time-of-flight mass spectrometry combined with a soft ionisation technique is expedient to analyse complex mixtures such as tobacco smoke with a high time resolution. The objective of the study was to separate pyrolysis from combustion processes to reveal the formation mechanism of several selected toxicants. A purposely designed adapter, with no measurable dead volume or memory effects, enables the analysis of pyrolysis and combustion gases from tobacco and tobacco products (e.g. 3R4F reference cigarette) with minimum aging. The combined system demonstrates clear distinctions between smoke composition found under air and nitrogen smoking atmospheres based on the corresponding mass spectra and visualisations using principal component analysis.     

Molecularly imprinted polymers on a silica surface for the adsorption of tobacco‐specific nitrosamines in mainstream cigarette smoke

Tobacco‐specific nitrosamines are one of the most important groups of carcinogens in tobacco products. Using adsorbents as filter additives is an effective way to reduce tobacco‐specific nitrosamines in cigarette smoke. Molecularly imprinted polymers (MIPs) using nicotinamide as template were grafted on the silica gel surface to obtain MIP@SiO₂ and employed as filter additives to absorb tobacco‐specific nitrosamines in mainstream cigarette smoke. Four milligrams of MIP@SiO₂ per cigarette was added to the interface between filter and tobacco rod to prepare a binary filter system. The mainstream smoke was collected on an industry‐standard Cambridge filter pad and extracted with ammonium acetate aqueous solution before analysis. Compared to the cigarette smoke of the control group, the levels of tobacco‐specific nitrosamines with silica gel and with MIP@SiO₂ were both reduced, and the adsorption rates of N‐nitrosonornicotine, N‐nitrosoanabasine, N‐nitrosoanatabine, and 4‐(methylnitrosamino)‐1‐(3‐pyridine)‐1‐butanone with silica gel and with MIP@SiO₂ were 20.76, 15.32, 18.79, and 18.01%, and 41.33, 34.04, 37.86, and 35.53%, respectively. Furthermore the content of total particle materials in cigarette smoke with silica gel was decreased evidently but showed no observable change with MIP@SiO₂. It indicated MIP@SiO₂ could selectively reduce tobacco‐specific nitrosamines in the mainstream cigarette smoke with no change to the cigarette flavor.     

卷烟主流烟气中氨的捕集及其离子色谱法测定

设计了高效的烟气捕集装置,建立了一种稀硫酸吸收、离子色谱法测定的卷烟主流烟气中氨的分析新方法.与早期的比色法、容量法、氨电极法、气相色谱法相比,该方法快速、简便,不需要复杂的样品前处理,完成一次分析只需12 min.检出限为0.005 mg/L,RSD为3.7%,空白加标回收率在87%～102%之间,吸烟加标回收率在98%～106%之间.测定了国内50种主要品牌卷烟,其主流烟气中氨含量范围为6.50～14.22μg/支烟.     

Risk Assessment of Passive Smoking Based on Analysis of Hair Nicotine and Cotinine as Exposure Biomarkers by In-Tube Solid-Phase Microextraction Coupled On-Line to LC-MS/MS

Passive smoking due to environmental tobacco smoke is a serious public health concern because it increases the risk of lung cancer and cardiovascular disease. However, the current status and effect of passive smoking in various lifestyles are not fully understood. In this study, we measured hair nicotine and cotinine levels as exposure biomarkers in non-smokers and assessed the risk from the actual situation of passive smoking in different lifestyle environments. Nicotine and cotinine contents in hair samples of 110 non-smoker subjects were measured by in-tube solid-phase microextraction with on-line coupling to liquid chromatography-tandem mass spectrometry, and self-reported lifestyle questionnaires were completed by the subjects. Nicotine and cotinine were detected at concentrations of 1.38 ng mg⁻¹ and 12.8 pg mg⁻¹ respectively in the hair of non-smokers, with levels significantly higher in subjects who reported being sensitive to tobacco smoke exposure. These levels were also affected by type of food intake and cooking method. Nicotine and cotinine in hair are useful biomarkers for assessing the effects of passive smoking on long-term exposure to environmental tobacco smoke, and our analytical methods can measure these exposure levels in people who are unaware of passive smoking. The results of this study suggest that the environment and places of tobacco smoke exposure and the lifestyle behaviors therein are important for the health effects of passive smoking.     

Puff-by-puff resolved characterisation of cigarette mainstream smoke by single photon ionisation (SPI)-time-of-flight mass spectrometry (TOFMS): comparison of the 2R4F research cigarette and pure Burley, Virginia, Oriental and Maryland tobacco cigarettes

Soft single photon ionisation (SPI)-time-of-flight mass spectrometry (TOFMS) is applied for the characterisation and comparison of puff-by-puff resolved and total yields of cigarette mainstream smoke from single tobacco type cigarettes (Virginia, Oriental, Burley, and Maryland) and the 2R4F University of Kentucky research cigarette. Puff-by-puff characteristics of various smoke components within one cigarette type as well as between different cigarette types can differ tremendously. This is demonstrated by means of a few selected compounds. Puff yields vary between 15 and 106 μm for acetaldehyde, 6 and 57 μm for NO, and between 1 and 8 μm for butadiene. Thereby, cigarettes containing 100% Oriental and Burley tobacco exhibit a very unique behaviour for the first and last puff. Different cultivation and processing methods as well as burning characteristics are most likely responsible for this. Since the 2R4F cigarette contains all four tobacco types it combines features of all of them. However, for some smoke constituents, smoking of the 2R4F reference cigarette results in exceptionally high yields which might not be attributable to the four pure tobacco types, but to other factors. In addition, comparison of the different cigarettes was also carried out by normalising the yields to puff resolved particulate matter. This procedure minimises effects caused by unequal smoke formation and represents another approach in evaluating the data.     

Determination of trace element concentrations of indian cigarette tobacco by instrumental neutron activation analysis

Lung cancer and smoking are associated. Epidemiological studies show that not only lung cancer but other chest diseases have causative relationship with smoking. Cigarette tobacco and smoke contains many carcinogens. Inorganic and metallic constituents of cigarette tobacco and smoke have not been studied as extensively as the organic compounds. Since some of the metals are highly toxic and also carcinogenic, authors have attempted to measure the levels of some of the trace elements of Indian tobacco by instrumental neutron activation analysis, and compared the results with the tobacco of America, Germany, Iran and New Zealand.     

Time-resolved analysis of the emission of sidestream smoke (SSS) from cigarettes during smoking by photo ionisation/time-of-flight mass spectrometry (PI-TOFMS): towards a better description of environmental tobacco smoke

In this study, the chemical composition of sidestream smoke (SSS) emissions of cigarettes are characterised using a laser-based single-photon ionisation time-of-flight mass spectrometer. SSS is generated from various cigarette types (2R4F research cigarette; Burley, Oriental and Virginia single-tobacco-type cigarettes) smoked on a single-port smoking machine and collected using a so-called fishtail chimney device. Using this setup, a puff-resolved quantification of several SSS components was performed. Investigations of the dynamics of SSS emissions show that concentration profiles of various substances can be categorised into several groups, either depending on the occurrence of a puff or uninfluenced by the changes in the burning zone during puffing. The SSS emissions occurring directly after a puff strongly resemble the composition of mainstream smoke (MSS). In the smouldering phase, clear differences between MSS and SSS are observed. The changed chemical profiles of SSS and MSS might be also of importance on environmental tobacco smoke which is largely determined by SSS. Additionally, the chemical composition of the SSS is strongly affected by the tobacco type. Hence, the higher nitrogen content of Burley tobacco leads to the detection of increased amounts of nitrogen-containing substances in SSS.     

离子色谱法测定卷烟主流烟气中氨含量的不确定度评定

根据《测量不确定度评定与表示》对离子色谱法测定卷烟主流烟气中氨含量的不确定度进行评定,通过分析得出,测量重复性、线性回归方程以及标准溶液的配制是不确定度的主要来源。分析结果结果表明,当卷烟样品主流烟气中氨释放量为12.04μg/支时,扩展不确定度为0.40μg/支,k=2。     

Hydrazine detection limits in the cigarette smoke matrix using infrared tunable diode laser absorption spectroscopy

Infrared absorption lines of hydrazine are broad and typically not baseline resolved, with line strengths approximately 100 times weaker than the more widely studied compound ammonia. Hardware and software improvements have been made to a two-color infrared tunable diode laser (IR-TDL) spectrometer in order to improve the limit of detection (LOD) of hydrazine (N2H4) in the cigarette smoke matrix. The detection limit in the smoke matrix was improved from 25 parts-per-million-by-volume (ppmv) to 4.2 ppmv using a 100 m pathlength cell with acquisition of background spectra immediately prior to each sample and 100 ms temporal resolution. This study did not detect hydrazine in cigarette smoke in the 964.4-964.9 cm(-1) spectral region, after mathematically subtracting the spectral contributions of ethylene, ammonia, carbon dioxide, methanol, acrolein, and acetaldehyde. These compounds are found in cigarette smoke and absorb in this spectral region. The LOD is limited by remaining spectral structure from unidentified smoke species. The pseudo random noise (root mean square) in the improved instrument was 2 x 10(-4) absorbance units (base e) which is equivalent to a 0.09 ppmv hydrazine gas sample in the multipass cell. This would correspond to a detection limit of 0.44 ppmv of hydrazine, given the dilution of the smoke by a factor of 5 by the sampling system. This is a factor of 10 less than the 4.2 ppmv detection limit for hydrazine in the smoke matrix, and indicates that the detection limit is primarily a result of the complexity of the matrix rather than the random noise of the TDL instrument.     

Multidimensional gas chromatographic determination of cotinine as a marker compound for particulate-phase environmental tobacco smoke

Multidimensional gas chromatographic analysis of air particles for the tobacco alkaloid cotinine is described. The analytical procedure requires little sample preparation. Unambiguous identification of cotinine and nicotine in cigarette smoke and indoor air samples was achieved by precise, reproducible retention times observed with two parallel analytical columns of different polarities and a nitrogen-specific detector. Further investigation of smoking and environmental variables is needed to validate the use of cotinine as a marker compound for environmental tobacco smoke particulate matter.     

High‐performance liquid chromatography with diode‐array detection cotinine method adapted for the assessment of tobacco smoke exposure

Smoking is considered to be one of the main risk factors for cancer and other diseases and is the second leading cause of death worldwide. As the anti‐tobacco legislation implemented in Europe has reduced secondhand smoke exposure levels, analytical methods must be adapted to these new levels. Recent research has demonstrated that cotinine is the best overall discriminator when biomarkers are used to determine whether a person has ongoing exposure to tobacco smoke. This work proposes a sensitive, simple and low‐cost method based on solid‐phase extraction and liquid chromatography with diode array detection for the assessment of tobacco smoke exposure by cotinine determination in urine. The analytical procedure is simple and fast (20 min) when compared to other similar methods existing in the literature, and it is cheaper than the mass spectrometry techniques usually used to quantify levels in nonsmokers. We obtained a quantification limit of 12.30 μg/L and a recovery of over 90%. The linearity ranges used were 12–250 and 250–4000 μg/L. The method was successfully used to determine cotinine in urine samples collected from different volunteers and is clearly an alternative routine method that allows active and passive smokers to be distinguished.