Collection and preparation of sidestream cigarette smoke for trace elemental determinations by graphite furnace atomic absorption spectrometry and inductively coupled plasma mass spectrometry.

A novel method for the collection and preparation of sidestream cigarette smoke condensate is described for trace elemental analysis by inductively coupled plasma mass spectrometry and graphite furnace atomic absorption spectrometry. The smoke collection method utilizes a specially designed chimney that collects and directs the sidestream smoke (SS) to a 2-stage trapping system consisting of an impaction trap followed by a 0.8 microm mixed cellulose ester filter. The samples are digested with nitric acid in a commercial heating block before analysis. The method limits of detection (LODs) are 1, 0.2, 2, 9, 6, and 7 ng/cigt for As, Cd, Pb, Ni, Se, and Cr, respectively. The SS collected from an industry reference cigarette, 1R4F, produced by the University of Kentucky was analyzed. The concentrations of As, Cd, and Pb in 1R4F were determined to be 27.3+/-2.1, 412+/-14, and 43.8+/-2.0 ng/cigt, respectively, while the concentrations of Ni, Cr, and Se are below the method LOD. Consequently, this novel method successfully addresses contamination, instrumentation, and collection issues for performing trace elemental analysis of sidestream cigarette smoke condensate.     

Separation and quantitation of phenolic compounds in mainstream cigarette smoke by capillary gas chromatography with mass spectrometry in the selected-ion mode

Cigarette smoke condensate is a complex chemical matrix and determination of phenolic compounds in it frequently requires extensive and laborious sample preparation. By utilizing derivatization techniques and capillary column gas chromatography with mass spectrometry in the selected-ion mode, separation and quantitation of selected phenolic compounds found in mainstream cigarette smoke can be accomplished with minimal sample preparation. This method has been used to determine concentrations of phenol, o-cresol, m-cresol, p-cresol, catechol, resorcinol and hydroquinone in cigarette smoke condensate from a number of commercially available cigarettes and a new cigarette which heats, but does not burn, tobacco. Unlike tobacco-burning cigarettes, levels of the phenolic compounds in the new cigarette smoke are at or below the detection limits for most of the compounds. This result is attributed to the unique design of the new cigarette.     

Determination of Cd levels in smoke condensate of Brazilian and Paraguayan cigarettes by Thermospray Flame Furnace Atomic Absorption Spectrometry (TS-FF-AAS)

In this study, the concentrations of Cd in smoke condensate of Paraguayan and Brazilian full flavor normal size cigarettes were determined. A “fishtail” chimney was used to confine and direct cigarette smoke to an impaction trap followed by 3 MCE (mixed cellulose ester) filters for smoke collection. The smoke condensate collected at the first two collection stages (chimney and impactor) was prepared as Triton X-100 slurry samples and the 3 MCE filters (third collection stage) used to collect smoke were microwave digested. Samples were analyzed by Thermospray Flame Furnace Atomic Absorption Spectrometry (TS-FF-AAS) for Cd and the results obtained were compared with Graphite Furnace Atomic Absorption Spectrometry (GFAAS). No significant differences were found between the values obtained with TS-FF-AAS and GFAAS at a 95% confidence level. The total concentration of Cd in the smoke of Brazilian and Paraguayan cigarettes tested ranged from 187 to 281 ng/cigarette and from 176 to 271 ng/cigarette, respectively. The LODs for Cd using TS-FF-AAS and GFAAS, were 5.8 and 1.5 ng/cigarette, respectively, for the analysis of smoke condensate from 1 cigarette. The main advantages of using the simple TS-FF-AAS system are its low running costs and the analysis time when compared to GFAAS.     

Determination of trace elements in total particulate matter of cigarette smoke by instrumental neutron activation analysis

Trace elements play an important role in the metabolism of the human body. Some of the trace elements are essential, whereas others are toxic and even carcinogenic. Cigarette smoke contains many of these hazardous trace elements. Tobacco samples have been analyzed by the authors for their trace element contents and the results have been reported earlier. This paper presents results on the trace element content analyzed in cigarette smoke using an automatic smoking machine developed in this laboratory to simulate actual smoking pattern. The trace element levels in the total particulate matter samples of the cigarette smoke collected on filter papers were measured and compared with those of cigarette smoke condensate reported in the literature. Both methods of collection give comparable results.     

Nachweis von Dibenzofuranen im Zigarettenrauchkondensat von Virginiatabak mittels Kapillargaschromatographie-Massenspektrometrie nach Wasserdampfdestillation sowie dünnschichtund hocheistungsflüssigkeitschromatographischer Abtrennung

Zusammenfassung Dibenzofuran und die vier isomeren Monomethyldibenzofurane wurden aus dem Zigarettenrauchkondensat von Virginiatabak mittels Wasserdampfdestillation, Dünnschichtchromatographie, Hochleistungsflüssigkeitschromatograhpie und Gaschromatographie abgetrennt. Charakterisierung und Identifizierung erfolgten durch Kapillargaschromatographie-Massenspektrometrie, sowie durch UV-Spektrometrie und durch den Vergleich chromatographischer Daten unter Zuhilfenahme authentischer Vergleichssubstanzen.

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Determination of dibenzofurans in cigarette smoke condensate of virginia tobaccos by means of gaschromatography — Mass spectrometry after separation by steam distillation, thin-layer chromatography and high-performance-liquid chromatograpby

Summary Dibenzofuran and the four isomers of monomethyldibenzofuran were isolated from cigarette smoke condensate of Virginia tobaccos by means of steam distillation, thin-layer chromatography and high performance-liquid chromatography. The characterization and identification were mainly achieved by capillary gaschromatography in combination with mass spectrometry as well as by comparison of Chromatographie retention data applying the respective substances as standards.

     

Investigations on the direct introduction of cigarette smoke for trace elements analysis by inductively coupled plasma mass spectrometry

Direct introduction of mainstream cigarette smoke into an inductively coupled plasma mass spectrometry (ICP-MS) has been investigated with respect to its feasibility for on-line analysis of trace elements. An automated apparatus was designed and built interfacing a smoking machine with an ICP-MS for smoke generation, collection, injection and analysis. Major and minor elements present in the particulate phase and the gas phase of mainstream cigarette smoke of 2R4F reference cigarettes have been qualitatively identified by examination of their full mass spectra. This method provides a rapid-screening analysis of the transfer of trace elements into mainstream smoke during cigarette combustion. A full suite of elements present in the whole cigarette smoke has been identified, including As, B, Ba, Br, Cd, Cl, Cs, Cu, Hg, I, K, Li, Mn, Na, Pb, Rb, Sb, Sn, Tl and Zn. Of these elements, the major portions of B, Ba, Cs, Cu, K, Li, Mn, Na, Pb, Rb, Sn, Tl and Zn are present in the particulate phase, whereas the major portion of Hg is present in the gas phase. As, Br, Cd, Cl, I and Sb exist in a distribution between the gas phase and the particulate phase. Depending on the element, the precision of measurement ranges from 5 to 25% in terms of relative standard deviation of peak height and peak area, based on the fourth puff of 2R4F mainstream cigarette smoke analyzed in five smoking replicates.     

烟气中有机酸的分析

 应用甲酯衍生化试剂对卷烟烟气粒相物中有机酸进行甲酯衍生化 ,经固相微萃取 (SPME)后通过气 质联用仪分离鉴定。分析了 4个品牌的卷烟烟气 ,共鉴定了 60多种挥发及半挥发性有机酸。对丁酸、己酸、糠酸、辛酸、壬酸、苯甲酸、苯乙酸、十四酸、十六酸进行了定量分析。该方法用于烟气中有机酸的定性、定量分析 ,灵敏度较高 ,快速简便。     

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/质谱联用仪上检测. 一氧化碳使用吸烟机自带的非散射红外检测器检测. 试验结果表明,与检测卷烟烟气中6种相关成分的烟草行业标准方法相比,简化了分析程序,避免重复抽吸卷烟的捕集步骤,得到的NNK相对标准偏差(RSD)小于6.0%,其它检测结果的RSD均小于3.0%,方法精密度良好,适合卷烟主流烟气中相关成分含量的测定.     

Quantification of 16 polycyclic aromatic hydrocarbons in cigarette smoke condensate using stable isotope dilution liquid chromatography with atmospheric‐pressure photoionization tandem mass spectrometry

A stable isotope dilution liquid chromatography tandem mass spectrometry method for the analysis of 16 polycyclic aromatic hydrocarbons in cigarette smoke condensate was developed and validated. Compared with previously reported methods, this method has lower limits of detection (0.04–1.35 ng/cig). Additionally, the proposed method saves time, reduces the number of separation steps, and reduces the quantity of solvent needed. The new method was applied to evaluate polycyclic aromatic hydrocarbon content in 213 commercially available cigarettes in China, under the International Standardization Organization smoking regime and the Health Canadian intense smoking regime. The results showed that the total polycyclic aromatic hydrocarbon content was more than two times higher in samples from the Health Canadian intense smoking regime than in samples from the International Standardization Organization smoking regime (1189.23 versus 2859.50 ng/cig, p < 0.05). Meanwhile, the concentration of individual polycyclic aromatic hydrocarbons (and total polycyclic aromatic hydrocarbons) increased with labeled tar content in both of the tested smoking regimes. There was a positive correlation between total polycyclic aromatic hydrocarbons under the International Standardization Organization smoking regime with that under the Health Canadian intense smoking regime. The proposed liquid chromatography tandem mass spectrometry method is satisfactory for the rapid, sensitive, and accurate quantitative evaluation of polycyclic aromatic hydrocarbon content in cigarette smoke condensate, and it can be applied to assess potential health risks from smoking.     

Optimization and validation of a gas chromatographic method for analysis of (RS,SR)-diastereoisomeric impurity in formoterol fumarate

The levels of 2-amino-9H-pyrido[2,3-b]indole (AalphaC or 2-amino-alpha-carboline), 2-amino-3-methyl-9H-pyrido[2,3-b]indole (MeAalphaC or 2-amino-3-methyl-alpha-carboline), 9H-pyrido[3,4-b]indole (norharman), and 1-methyl-pyrido[3,4-b]indole (harman) have been determined in the mainstream smoke condensate from three reference cigarettes, namely Kentucky reference 1R5F, Kentucky reference 2R4F, and CORESTA CM4. The amino-alpha-carbolines, and norharman and harman (beta-carbolines) can be classified as heterocyclic aromatic amines (HAAs) and are listed as biologically active agents in the mainstream smoke of cigarettes. For the analysis, the mainstream smoke condensate from cigarettes was collected on a filter pad, the analytes were isolated using solid-phase extraction (SPE), and quantified without derivatization on a GC-MS. Total amounts of carbolines found in the condensate increased from ultralight 1R5F to full-flavor CM4 cigarettes. The level of harman was about 250 ng/cigarette for the 1R5F cigarette and about 1025 ng/cigarette for the CM4 cigarette. Norharman was typically three times more abundant than harman. The AalphaC was found at about 10 times lower level compared to harman, and MeAalphaC was about 50 times lower than harman. The use of reference cigarettes can provide a common measure for laboratories to assess carboline amounts among cigarette brands.     

High-pressure liquid chromatography of polynuclear aromatic hydrocarbons of cigarette smoke condensate

Reverse-phase, high-pressure liquid chromatography (h.p.l.c.) on Permaphase ODS and ETH was applied to the fractions of cigarette smoke condensate containing polynuclear aromatic hydrocarbons (PAH). A PAH-enriched fraction was first separated by gel filtration, and selected fractions were subjected to h.p.l.c. Although standard PAH could be easily separated on Permaphase ODS, results with smoke condensate were unsatisfactory. Better results were obtained with Permaphase ETH, which gave sufficient resolution for identification. PAH identification was aided by means of a stop-flow technique and measurement of the u.v. spectra of eluting peaks. Benzo(a)pyrene in the smoke condensate could be determined. However, for resolution of the PAH in smoke condensates, the total overall performance of h.p.l.c. was judged inferior to that of gas chromatography.     

Determination of toxic elements in tobacco products by instrumental neutron activation analysis

The concentration of 15 elements in various brands of cigarette tobacco and cigarette wrapping paper were determined using instrumental neutron activation analysis. The paper of some of the brands contains higher concentrations of toxic elements than the tobacco. The cigarette filter and the ash were also analyzed to determine the adsorption of toxic elements on the filter and their transference in smoke. The toxic effects of some of the elements have been briefly discussed.     

Separation and quantitation of monovalent anionic and cationic species in mainstream cigarette smoke aerosols by high-performance ion chromatography

A simple method has been developed to separate and quantitate monovalent ionic species in mainstream cigarette smoke aerosols based on ion chromatography (IC) with conductivity detection. The method entails collecting the smoke aerosol particulate phase by electrostatic precipitation, dissolving the smoke condensate in methanol (MeOH), and separating the ionic species on either a cation- or anion-exchange column. The method has been applied to the analysis of smoke aerosols from two cigarettes, 1R4F Kentucky Reference cigarettes and a new cigarette that heats but does not burn tobacco. The predominant cations in smoke aerosols from 1R4F Kentucky Reference and the new cigarettes are sodium (Na+), ammonium (NH4+), and potassium (K+) ions; the predominant anions are acetate (AcO-) and formate (HCOO-). Trace amounts of chloride (Cl-), nitrite (NO2-), and nitrate (NO3-) ions are also present.     

Analytical study of cigarette smoke enriched in benzo[a]pyrene for use in model animal studies

Cigarette smoke has been significantly enriched in benzo[a]pyrene (BAP) by injecting 200 μl of a cyclohexane solution, containing a total of 40 μg of BAP, into a cigarette. After injection, the cigarette is conditioned and smoked according to standard protocol. When the cigarette smoke condensate is analyzed by fluorescence spectroscopy, liquid scintillation counting, gas chromatography with flame ionization detection, and gas chromatography-mass spectrometry, it is found that the level of BAP has increased by 1000 times with respect to levels reported for unenriched cigarette smoke. No chemical transformation of the BAP has been detected, and the BAP-enriched fraction does not appear to be perturbed to a detectable degree. Approximately 28% of the BAP is measured in the mainstream smoke, 46–48% in the sidestream smoke from the burning end of the cigarette, and 7% in the butt and ash. Correcting for analytical losses, about 10% appears to escape in the gaseous state. This material may prove suitable for model animal studies.     

Quantitative determination of selected compounds in a Kentucky 1R4F reference cigarette smoke by multidimensional gas chromatography and selected ion monitoring-mass spectrometry

Eight compounds from a Kentucky 1R4F reference cigarette smoke condensate have been determined by selected ion monitoring-mass spectrometry (SIM-MS) to confirm the validity of multidimensional gas chromatography (MDGC) as a quantitative tool in complex mixture analyses. Four electrostatically precipitated smoke condensate samples of 100 cigarettes each are dissolved individually in 25 mL of 2-propanol. The 2-propanol contains two methyl esters (C8 and C14) and seven deuterium-labeled compounds used as internal standards (IS). Analysis of the compounds of interest, pyridine; acetamide; acrylamide; phenol; o-, m-, and p-cresol; and quinoline, is accomplished by using two heartcuts. Heartcut times of the MDGC analysis are selected such that at least one IS is transferred with each group of compounds being analyzed. This study shows that the MDGC technique previously developed and described can be used for quantitative analyses. A comparison is made between the two types of internal standards. The results obtained for both types of internal standards agree within 20% of each other, on the average, with higher standard deviations for approximately 60% of the compounds where methyl esters are used as internal standards.     

离子色谱法测定卷烟主流烟气中的硫化氢

建立了测定卷烟主流烟气中硫化氢含量的离子色谱法.采用玻璃纤维滤片捕集卷烟烟气粒相物,并用0.5%(体积分数)乙二胺-50 mmol/L氢氧化钠-250 mmol/L乙酸钠溶液萃取粒相物,吸收液吸收气相物中的硫化氢,合并粒相萃取液与气相吸收液,经离子色谱柱分离,以1.5 mol/L氢氧化钠-1 mol/L乙酸钠-2%(体积分数)乙二胺(40∶50∶10,体积比)为流动相,安培检测器检测并施加-100 mv的检测电位.运用方法对12种市售卷烟样品进行了测定,结果表明:方法的线性范围为0.1~5.0μg/mL,检出限为1.03μg/mL,定量限为3.41μg/mL,回收率为102.3%~107.2%,相对标准偏差小于5%.方法处理简单、准确度高,可以用于卷烟烟气中硫化氢含量的测定.     

Tobacco smoke chemistry 3. Aromatic acids of cigarette smoke condensate

A fraction containing mainly aromatic acids has been isolated from cigarette smoke condensate. Gas chromatographic and mass spectral analysis of the corresponding methyl esters and comparison with reference compounds, many of which were synthesized for this purpose, made possible the identification of 27 constituents (Table 1). Eighteen of these have not been detected in tobacco smoke condensate before.     

Gas chromatography-mass spectrometry of carbonyl compounds in cigarette mainstream smoke after derivatization with 2,4-dinitrophenylhydrazine

An improved gas chromatography-mass spectrometry (GC-MS) method was described for the analysis of carbonyl compounds in cigarette mainstream smoke (CMS) after 2,4-dinitrophenylhydrazine (DNPH) derivatization. Besides formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde, methyl ethyl ketone, butyraldehyde, and crotonaldehyde that are routinely analyzed in cigarette smoke, this technique separates and allows the analysis of several C4, C5 and C6 isomeric carbonyl compounds. Differentiation could be made between the linear and branched carbon chain components. In cigarette smoke, the branched chain carbonyls are found at higher level than the linear chain carbonyls. Also, several trace carbonyl compounds such as methoxyacetaldehyde were found for the first time in cigarette smoke. For the analysis, cigarette smoke was collected using DNPH-treated pads, which is a simpler procedure compared to conventional impinger collection. Thermal decomposition of DNPH-carbonyl compounds was minimized by the optimization of the GC conditions. The linear range of the method was significantly improved by using a standard mixture of DNPH-carbonyl compounds instead of individual compounds for calibration. The minimum detectable quantity for the carbonyls ranged from 1.4 to 5.6 microg/cigarette.     

聚丙烯腈和二氧化硅复合纤维膜富集-高分辨质谱法测定烟气中的有害化合物

以聚丙烯腈(PAN)和二氧化硅(Si02)纳米粒子的混合溶液为纺丝溶液,采用静电纺丝技术制备具有高吸附性能的新型PAN-SiO2疏水性复合纤维膜,对香烟燃烧产生的烟气进行富集,用甲醇作为洗脱溶剂,对待测组分进行洗脱,并使用高分辨串联质谱技术进行测定.实验结果表明,通过调控PAN和SiO2纳米粒子的浓度,优化静电纺丝参数,得到对小分子有机化合物吸附性较强的纤维膜.对所收集到的烟气进行质谱测定,在正离子模式下,检测到的主要成分有尼古丁、丙酮、苯乙烯、丙烯醛、异戊二烯、丙烯腈等21种小分子有机化合物;在负离子模式下,检测到的主要成分有水杨酸、苹果酸和乳酸等6种有机酸.同时,对烟气中的主要有害成分尼古丁进行定量分析,方法的检出限为0.071 ng/L,定量限为0.236 ng/L.