The Distribution of Total Particulate Matter (TPM) And Nicotine Between Mainstream and Sidestream Smoke in Bidis and Cigarettes

ABSTRACT

The mainstream (MS) and sidestream (SS) smoke of three types of popular Indian cigarettes, a brand of low tar Indian cigarettes, a brand of US cigarettes and two brands of popular Indian bidis were analysed for carcinogenic total particulate matter (TPM) and nicotine levels employing standard smoking conditions and/or modified smoking standards.

The analysis clearly demonstrated relatively higher levels of TPM and nicotine in MS of three types of popular Indian cigarettes when compared with a brand of low tar Indian cigarettes or a brand of US cigarettes or reported values for MS of western cigarettes. This was also reflected in MS/SS ratios of TPM and nicotine as TPM and nicotine levels in SS of Indian and US cigarettes were similar, when tested employing standard smoking conditions.

Comparative analysis of Indian bidis/cigarettes and a brand of US cigarettes employing modified smoking standard (i.e. 2 puffs/min instead of 1 puff/min) revealed significantly lower values of TPM and nicotine in SS of Indian bidis when compared with corresponding values in Indian/US cigarettes. This shows that contribution of TPM and nicotine in SS from a single bidi to environmental tobacco smoke (ETS) is very much less than that of a single cigarette, and contribution of SS from Indian and US cigarettes to ETS appear to be similar. Reduced levels of TPM and nicotine in SS of bidis, probably due to lack of added burning agents, result into relatively higher deliveries of TPM and nicotine in MS as reflected by higher MS/SS values.     

Determination of the elemental distribution in cigarette components and smoke by instrumental neutron activation analysis

Cigarette smoking is a major source of particles released in indoor environments. A comprehensive study of the elemental distribution in cigarettes and cigarette smoke has been completed. Specifically, concentrations of thirty elements have been determined for the components of 15 types of cigarettes. Components include tobacco, ash, butts, filters, and cigarette paper. In addition, particulate matter from mainstream smoke (MS) and sidestream smoke (SS) were analyzed. The technique of elemental determination used in the study is instrumental neutron activation analysis. The results show that certain heavy metals, such as As, Cd, K, Sb and Zn, are released into the MS and SS. These metals may then be part of the health risk of exposure to smoke. Other elements are retained, for the most part, in cigarette ash and butts. The elemental distribution among the cigarette components and smoke changes for different smoking conditions.     

Intra-puff CO and CO2 measurements of cigarettes with iron oxide cigarette paper using quantum cascade laser spectroscopy

The objective of this research was to apply Fourier transform infrared spectroscopy (FTIR) and tunable infrared laser differential absorption spectroscopy (TILDAS) for measuring selected gaseous constituents in mainstream (MS) and sidestream (SS) smoke for experimental cigarettes designed to reduce MS CO using iron oxide cigarette papers. These two complimentary analytical techniques are well suited for providing per puff smoke deliveries and intra-puff evolution profiles in cigarette smoke respectively. The quad quantum cascade (QC) laser high resolution infrared spectroscopy system has the necessary temporal and spectral resolution and whole smoke analysis capabilities to provide detailed information for CO and CO(2) as they are being formed in both MS and SS smoke. The QC laser system has an optimal data rate of 20 Hz and a unique puffing system, with a square wave shaped puff, that allows whole smoke to enter an 18 m, 0.3 L multi-pass gas cell in real time (0.1s cell response time) requiring no syringe or Cambridge filter pad. Another similar multi-pass gas cell with a 36 m pathlength simultaneously monitors the sidestream cigarette smoke. The smoke from experimental cigarettes manufactured with two types of iron oxide papers were compared to the smoke from cigarettes manufactured similarly without iron oxide in the paper using both instrument systems. The delivery per puff determined by the QC laser method agreed with FTIR results. MS CO intra-puff evolution profiles for iron oxide prototype cigarettes demonstrated CO reduction when compared to cigarettes without iron oxide paper. Additionally, both CO and CO(2) intra-puff evolution profiles of the cigarettes with iron oxide paper showed a significant reduction at the initial portion of the 2 s puff not observed in the non-iron oxide prototype cigarettes. This effect also was observed for ammonia and ethylene, suggesting that physical parameters such as paper porosity and burn rate are important. The SS CO and CO(2) deliveries for the experimental cigarettes evaluated remained unaffected. The iron oxide paper technology remains under development and continues to be evaluated.     

An improved headspace solid-phase microextraction method for the analysis of free-base nicotine in particulate phase of mainstream cigarette smoke

The content of free-base nicotine in cigarette smoke is a controversial subject, partly due to methodological issues. In this investigation, an improved method to measure free-base nicotine in cigarette smoke using headspace solid-phase microextraction (HS-SPME) combined with GC/MS analysis, was developed and validated for this purpose. Cigarette smoke particulate phase (PP) was collected onto a 44 mm glass fiber filter pad. The pad was cut in halves with one half used to determine the concentrations of total nicotine and water. The remaining half was analyzed by HS-SPME for free-base nicotine. The following factors were found to have a significant impact on the responses of free-base nicotine: SPME fiber type, pre-equilibrium time before HS-SPME, extraction time and temperature, PP water content, and the solvent used for the preparation of standards. It was also found that the impact of PP water content on the determination of free-base nicotine from smoke sample could be corrected by a water correction factor calculated based on an experimentally determined reciprocal model. The precision of the method was evaluated with smoke samples of reference cigarettes: Canadian flue-cured monitor and Kentucky reference 2R4F. The RSD values obtained were in the 12.8-16.8% range.     

Analysis of aromatic amines in cigarette smoke

A method for the analysis of o-toluidine, o-anisidine, 2-naphthylamine, and 4-aminobiphenyl in cigarette mainstream smoke has been developed, which combines the sensitivity of their pentafluoropropionyl (PFP) derivatives in negative ion chemical ionization (NICI) mode with the selectivity of the gas chromatography/tandem mass spectrometry (GC/MS/MS) technique. The use of four deuterated analogues as internal standards along with the application of the standard addition method results in accurate and precise results; the interday precision for the aromatic amines was 3-10% and the accuracy ranged from 97-100%. This method was applied to two American-blend University of Kentucky reference cigarettes, eight American-blend market cigarettes, a bright (flue-cured) tobacco cigarette, and an electrically heated cigarette smoking system (EHCSS). For the American-blend cigarettes there was a linear correlation between aromatic amine yields and mainstream smoke 'tar' ('tar' = total particulate matter - (nicotine + water)), whereas the bright tobacco cigarette and the EHCSS demonstrated significantly lower aromatic amine yields on an equal 'tar' basis. The results support the hypothesis that the nitrogen content of the tobacco, and above all the cigarette combustion temperature, are determining factors for the yields of aromatic amines in smoke.     

Simultaneous determination of four tobacco-specific N-nitrosamines in mainstream smoke for Chinese Virginia cigarettes by liquid chromatography-tandem mass spectrometry and validation under ISO and “Canadian intense” machine smoking regimes

A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for determining four tobacco-specific N-nitrosamines (TSNAs) in mainstream smoke from Chinese Virginia cigarettes was developed. Mainstream cigarette smoke particulate matter was collected on a Cambridge filter pad, further extracted using 100 mM ammonium acetate after 100 μL internal standard addition, and subsequently analyzed with LC-MS/MS. The limit of detection for NNN, NNK, NAT and NAB were 0.006, 0.013, 0.003 and 0.021 ng mL⁻¹ respectively, with a linear calibration range spanning 1-200 ng mL⁻¹. Intra- and inter-day precision for four TSNAs ranged from 3.3% to 8.5% and 2.3% to 10.1%; recovery was between 89.1% and 104.9% for Chinese Virginia cigarettes. The proposed method was applied to evaluate TSNAs yields for 39 commercially available cigarettes in Chinese market under ISO and “Canadian intense” machine smoking regimes, on the ground that it comes closest to representing smoke deliveries from human smoking. Total TSNAs emissions are more than double under the Canadian regime. TSNAs:nicotine ratios were used in our assay to show any differences in yield from different brands. TSNAs:nicotine levels show more than a 10-fold difference across brands and types (Chinese Virginia cigarettes and blended cigarettes) in the Chinese market.     

Quad quantum cascade laser spectrometer with dual gas cells for the simultaneous analysis of mainstream and sidestream cigarette smoke

A compact, fast response, infrared spectrometer using four pulsed quantum cascade (QC) lasers has been applied to the analysis of gases in mainstream (MS) and sidestream (SS) cigarette smoke. QC lasers have many advantages over the traditional lead-salt tunable diode lasers, including near room temperature operation with thermoelectric cooling and single mode operation with improved long-term stability. The new instrument uses two 36 m, 0.3 l multiple pass absorption gas cells to obtain a time response of 0.1s for the MS smoke system and 0.4s for the SS smoke system. The concentrations of ammonia, ethylene, nitric oxide, and carbon dioxide for three different reference cigarettes were measured simultaneously in MS and SS smoke. A data rate of 20Hz provides sufficient resolution to determine the concentration profiles during each 2s puff in the MS smoke. Concentration profiles before, during and after the puffs also have been observed for these smoke constituents in SS smoke. Also, simultaneous measurements of CO(2) from a non-dispersive infrared (NDIR) analyzer are obtained for both MS and SS smoke. In addition, during this work, nitrous oxide was detected in both the MS and SS smoke for all reference cigarettes studied.     

Application of dosimetry tools for the assessment of e-cigarette aerosol and cigarette smoke generated on two different in vitro exposure systems

The diluted aerosols from a cigarette (3R4F) and an e-cigarette (Vype ePen) were compared in two commercially available in vitro exposure systems: the Borgwaldt RM20S and Vitrocell VC10. Dosimetry was assessed by measuring deposited aerosol mass in the exposure chambers via quartz crystal microbalances, followed by quantification of deposited nicotine on their surface. The two exposure systems were shown to generate the same aerosols (pre-dilution) within analytically quantified nicotine concentration levels (p = 0.105). The dosimetry methods employed enabled assessment of the diluted aerosol at the exposure interface. At a common dilution, the per puff e-cigarette aerosol deposited mass was greater than cigarette smoke. At four dilutions, the RM20S produced deposited mass ranging 0.1–0.5 µg/cm²/puff for cigarette and 0.1–0.9 µg/cm²/puff for e-cigarette; the VC10 ranged 0.4–2.1 µg/cm²/puff for cigarette and 0.3–3.3 µg/cm²/puff for e-cigarette. In contrast nicotine delivery was much greater from the cigarette than from the e-cigarette at a common dilution, but consistent with the differing nicotine percentages in the respective aerosols. On the RM20S, nicotine ranged 2.5–16.8 ng/cm²/puff for the cigarette and 1.2–5.6 ng/cm²/puff for the e-cigarette. On the VC10, nicotine concentration ranged 10.0–93.9 ng/cm²/puff for the cigarette and 4.0–12.3 ng/cm²/puff for the e-cigarette. The deposited aerosol from a conventional cigarette and an e-cigarette in vitro are compositionally different; this emphasises the importance of understanding and characterising different product aerosols using dosimetry tools. This will enable easier extrapolation and comparison of pre-clinical data and consumer use studies, to help further explore the reduced risk potential of next generation nicotine products.

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Graphical abstract A cigarette and an e-cigarette (top left) were assessed on two different in vitro exposure systems, the Borgwaldt RM20S (top right) and the VC 10 (bottom right). Compositionally the product aerosols were different, but there was no difference between the same product on different machines (bottom left).

     

Selective determination of tobacco‐specific nitrosamines in mainstream cigarette smoke by GC coupled to positive chemical ionization triple quadrupole MS

A rapid method for the selective determination of four kinds of tobacco‐specific nitrosamines, N‐nitrosonornicotine, N‐nitrosoanatabine, N‐nitrosoanabasine and 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanone, in mainstream cigarette smoke was developed by GC coupled to positive chemical ionization triple‐quadrupole MS. After mainstream cigarette smoke was collected on a cambridge filter pad, the particulate matter was extracted with 0.1 M HCL aqueous solution, cleaned by positive cation‐exchange solid extraction, and finally injected into GC–MS/MS using isotopically labeled analogues as internal standards. Excellent linearity was obtained over the concentration range of 0.5–200.0 ng mL^?1 for all tobacco‐specific nitrosamines with values for correlation coefficient between 0.9996–0.9999. Limits of detection of each tobacco specific nitrosamine varied from 0.023–0.028 ng cig^?1, and lower limits of quantification varied from 0.077–0.093 ng cig^?1. The recovery of each tobacco specific nitrosamine was from 90.0–109.0%. The relative standard deviations of the intra‐day and inter‐day precisions were 3.1–5.8 and 3.9–6.6, respectively. This method was applied to reference and domestic cigarettes. The result showed that the method was consistent with traditional methods and can be used as an effective approach for the routine analysis of tobacco‐specific nitrosamines.     

Liquid chromatography with tandem mass spectrometry method for the determination of nicotine and minor tobacco alkaloids in electronic cigarette refill liquids and second‐hand generated aerosol

A liquid chromatography with tandem mass spectrometry method for the simultaneous quantification of nicotine and seven minor tobacco alkaloids in both refill liquids for electronic cigarettes and their generated aerosol was developed and validated. The limit of detection and limit of quantification values were 0.3–20.0 and 1.0–31.8 ng/mL, respectively. Within‐laboratory reproducibility was 8.2–14.2% at limit of quantification values and 4.8–12.7% at other concentration levels. Interday recovery was 75.8–116.4%. The method was applied to evaluate the compliance of commercial liquids (n = 95) with their labels and to assess levels of minor alkaloids. Levels of nicotine and its corresponding compounds were also evaluated in generated aerosol. About 47% of samples showed differences above ±10 % of the stated nicotine concentration. About 78% of the “zero nicotine” liquids showed traces in the range of 1.3 ± 0.1–254.0 ± 14.6 μg/mL. Nicotine‐N ′‐oxides, myosmine, and anatabine were the most common minor alkaloids in liquids containing nicotine. Nicotine and N ′‐oxides were detected in all air samples when aerosol was generated from liquids containing nicotine. Nicotine average emissions from electronic cigarette (2.7 ± 0.9 μg/m³) were significantly lower (p < 0.01, t‐test) with respect to conventional cigarette (30.2 ± 1.5 μg/m³).     

Rapid and sensitive method for simultaneous determination of six carcinogenic aromatic amines in mainstream cigarette smoke by liquid chromatography/electrospray ionization tandem mass spectrometry

Aromatic amines are one of the sources of carcinogenicity in cigarette and tobacco smoke. Accurate quantification of these chemicals is needed to assess public health risk. A new validated rapid, sensitive and analyte specific liquid chromatography/electrospray ionization tandem mass spectrometric (LC/MS/MS) method has been developed for the simultaneous determination of six aromatic amines in mainstream cigarette smoke using research reference cigarette 2R4F. Three popular Indian brand cigarettes were also analyzed using the same procedure. The limit of detection of this method ranged from 0.04 to 0.59 ng/cig using an injection volume of 7 μl. The identification of each amine was established by chromatographic retention times, analyte specific fragmentation pattern and relative peak area ratios of two product/precursor ion pairs. The method showed excellent reproducibility and was also rapid, selective and robust for aromatic amine determination from cigarette smoke.     

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     

Analysis of the Heterocyclic Aromatic Amines in Cigarette Smoke by Liquid Chromatography–Tandem Mass Spectrometry

In this paper, a sensitive accurate method for the determination of heterocyclic aromatic amines (HAAs) in cigarette smoke has been developed and validated using solid-phase extraction coupled with liquid chromatography–tandem mass spectrometry. A calibration curve was obtained with representative cigarette smoke using the standard addition method to compensate for matrix effects because the smoke of different cigarettes shows similar matrix effects. With this method, the accuracy of the method can be improved using a common analog of HAAs, which will greatly reduce the expense of using an isotope-labeled internal standard. Validation results showed that the method has high sensitivity (quantification limits of 0.08–0.56 ng cig⁻¹), good reproducibility (RSD 6.37–9.31 %) and satisfactory recoveries (81.0–111 %). With this method, the emissions of HAAs in 30 commercial cigarette samples were analyzed and compared.

     

Determination of Nicotine in Tobacco by Capillary Electrophoresis with Electrochemical Detection

A sensitive, simple and low-cost method based on capillary electrophoresis(CE) with electrochemical(EC) detection at a carbon fiber microdisk electrode(CFE) was developed for the determination of nicotine. Effects of detection potential, concentration and pH value of the phosphate buffer, and injection time as well as separation voltage were investigated. Under the optimized conditions: a detection potential of 1.20 V, 40 mmol/L phosphate buffer(pH 2.0), a sample injection time of 10 s at 10 kV and a separation voltage of 16 kV, the linear range obtained was from 5.0×10^-7 mol/L to 1.0×10^-4 mol/L with a correlation coefficient of 0.9989 and the limit of detection(LOD, S/N=3) obtained was 5.0×10^-8 mol/L. The method was also used to determine the nicotine in cigarettes. Nicotine amount ranged from 0.211 mg/g to 0.583 mg/g in the pipe tobacco of seven brands of cigarette and the amount in one cigarette varied from 0.136 mg/cigarette to 0.428 mg/cigarette.     

液相色谱-串联质谱法测定卷烟主流烟气中的四种致癌物

N-亚硝基降烟碱（NNN）、4-（亚硝基甲氨基）-1-（3-吡啶基）-1-丁酮（NNK）、N-亚硝基新烟草碱 （NAT）和N-亚硝基假木贼碱（NAB）是4种广泛存在于烟草和烟气中的致癌物,准确测定其含量对评估其对人体健康的影响有着重要的作用。采用液相色谱-电喷雾串联质谱(LC-ESI MS/MS)技术建立了卷烟主流烟气中NNN、NNK、NAT和NAB的测定方法,并将其用于中国烤烟和混合型卷烟主流烟气的分析。卷烟主流烟气通过剑桥滤片捕集,捕集烟气后的滤片在加入100 μL氘代混合内标后用10 mL 100 mmol/L醋酸铵水溶液萃取,萃取液过水相滤膜后直接进行LC-ESI MS/MS检测。选用Agilent Zorbax Eclipse XDB-C18色谱柱,以流动相0.1%(v/v)乙酸水溶液和0.1%（v/v）乙酸甲醇溶液梯度洗脱,质谱检测采用正离子扫描,多反应监测模式。NNN、NNK、NAT和NAB的检出限分别为0.019、0.002、0.008和0.007 μg/L,回收率为84.9%～104.5%,相对标准偏差(n=8)为2.96%～6.65%。该方法的检出限低,特异性好,适用于卷烟主流烟气中NNN、NNK、NAT和NAB释放量的检测。     

Analysis of the Heterocyclic Aromatic Amines in Cigarette Smoke by Liquid Chromatography–Tandem Mass Spectrometry

In this paper, a sensitive accurate method for the determination of heterocyclic aromatic amines (HAAs) in cigarette smoke has been developed and validated using solid-phase extraction coupled with liquid chromatography–tandem mass spectrometry. A calibration curve was obtained with representative cigarette smoke using the standard addition method to compensate for matrix effects because the smoke of different cigarettes shows similar matrix effects. With this method, the accuracy of the method can be improved using a common analog of HAAs, which will greatly reduce the expense of using an isotope-labeled internal standard. Validation results showed that the method has high sensitivity (quantification limits of 0.08–0.56 ng cig^?1), good reproducibility (RSD 6.37–9.31 %) and satisfactory recoveries (81.0–111 %). With this method, the emissions of HAAs in 30 commercial cigarette samples were analyzed and compared.     

Effects of common ammonium salt on the thermal behavior of reconstituted tobacco sheet

Understanding the role of chemical burn additives on modifying the toxic gaseous constituents and thermal behavior of reconstituted tobacco sheet (RTS) has recently taken center stage through a number of initiatives. In this current study, the effects of ammonium chloride (AC), ammonium sulfate, diammonium phosphate, and monoammonium phosphate on the formation of evolved gaseous products, specifically carbonyl compounds and thermal behavior were investigated. Results on cigarette smoking tests revealed that ammonium salt was a potential burn additive to reduce carbonyl compounds delivery in the cigarette mainstream smoke of RTS. The yield per puff of carbonyl compounds of pure RTS was decreased from 247.8 µg to 133.30 µg with the incorporation of AC. Thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) were used to investigate the thermal decomposition of RTS. TG results revealed that the incorporation of ammonium salt into RTS could improve the thermal stability of RTS. The DSC results showed that the maximum exothermic peak was drastically decreased with the addition of ammonium salt, for example, from 14.8 mW mg^?1 of pure RTS to 10.27 mW mg^?1 of AC-RTS. Results on Fourier transform infrared spectrometer (FTIR) which was employed to investigate the generation of evolved volatile products showed that these four ammonium salts as burn additives were efficiently high enough to decrease the formation of gaseous products. From our findings, compared with the virgin RTS and other three modified RTS, AC-RTS could significantly decrease the yields of nicotine and phenolic compounds in the cigarette mainstream smoke of RTS.     

Determination of Acrylamide and Acrolein in Smoke from Tobacco and E-Cigarettes

Acrylamide and acrolein are two short-chained hazardous compounds with neurotoxic, carcinogenic, and mutagenic effects. The aim of this paper is to describe a fast and simple procedure for simultaneous determination of both acrylamide and acrolein under standard conditions, suggest a suitable calibration protocol for custom analysis, and demonstrate its applicability to the analysis of gaseous products from, e.g., cigarettes, cigars, or electronic cigarettes. A gas chromatography–mass spectrometry (GC–MS) method was developed to quantify acrylamide and acrolein in smoke vapor from electronic cigarettes, tobacco cigarettes, and cigars. Nonionic and highly polar molecules with a low boiling point and molecular mass need a suitable derivatization method to achieve appropriate retention and selectivity on commonly used relatively nonpolar stationary phases and to enhance the molecular mass for easy MS detection. The derivatization of acrylamide and acrolein was carried out by a bromination method with elemental bromine. The dibromo derivatives were extracted into an organic solvent and following a dehydrobromination procedure the samples were injected into the GC–MS system. Important experimental parameters were varied, after which the bromination time was defined as 30 min, and the injector temperature and the starting temperature of gradient were set at 280 and 50 °C respectively. Acrolein was found in all tested samples, while acrylamide was detected only in smoke from normal tobacco. Possible mechanisms for the formation of these unsaturated compounds in the samples are discussed. After its validation the newly developed method was successfully and reliably applied to the analysis of both compounds. This short method provides an easy way to determine acrylamide and acrolein in gaseous samples.