Fractionation of cadmium in tobacco and cigarette smoke condensate using XANES and sequential leaching with ICP-MS/MS
Fractionation data for cadmium in tobacco products, as obtained by sequential leaching of cadmium species with ICP-MS/MS analysis, and separately by X-ray absorption near edge structure (XANES) are presented here for the first time. The total amount of cadmium found in 3R4F cigarette cut tobacco was 1526 ± 42 μg kg−1, of which 5% was found in the smoke under ISO smoking conditions. XANES analysis showed that Cd in tobacco, cigarette smoke and ash was present in the + 2 oxidation state. Examination of the gas-particle partitioning of smoke cadmium suggests that Cd in mainstream smoke is best viewed as semi-volatile, existing in both particulate and gas phases. Sequential extraction of trapped tobacco smoke was carried out to get a deeper insight into the chemistry of cigarette smoke cadmium compounds. Consecutive extractions with ultrapure water, dilute (1%) nitric acid and 10% nitric acid led to extraction of a total amount of Cd which agreed with that obtained after microwave digestion of the whole sample, suggesting that cadmium was quantitatively leachable into aqueous/acidic solutions. Most Cd (~ 90% of the total Cd in the smoke condensate) was extracted into dilute nitric acid (likely as CdO, Cd(OH)2 and CdCO3) with a minor percentage (3%) extracted into water (likely as CdCl2) and in 10% nitric acid (likely as CdS). Extraction of trapped mainstream smoke with pentane, followed by ICP-MS/MS analysis, to examine the possible presence of organocadmium in 3R4F tobacco smoke, did not show the presence of organocadmium compounds above the method LOQ (2 μg kg−1), possibly due to their reactivity under the experimental conditions. The high selectivity with sufficient sensitivity achieved by ICP-MS/MS was invaluable to quantify Cd (at low μg kg−1levels) simultaneously with sulphur and chlorine in the tobacco smoke fractions of complex matrix. The cadmium chemistry in the smoke, identified in this study, is consistent with both relatively high lung absorption and DNA binding; both potentially important factors for disease progression in smokers.
KeywordsMass spectrometry/ICP-MS Metals/heavy metals Trace elements
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
- 3.Food and Drug Administration. Harmful and potentially harmful constituents in tobacco products and tobacco smoke: established list. 2012. Available at:https://www.fda.gov/TobaccoProducts/GuidanceComplianceRegulatoryInformation/ucm29778. Accessed 21 March 2018.
- 4.Cuello S, Entwisle J, Benning J, Liu C, Coburn S, McAdam KG, et al. Complementary HPLC-ICP-MS and synchrotron X-ray absorption spectroscopy for speciation analysis of chromium in tobacco samples. J Anal At Spectrom. 2016;31:1818–29.Google Scholar
- 5.Taebunpakul S, Liu C, Wright C, McAdam K, Heroult J, Braybrook J, et al. Determination of total arsenic and arsenic speciation in tobacco products: from tobacco leaf and cigarette smoke. J Anal At Spectrom. 2011;26:1633–40.Google Scholar
- 11.Gondola I, Kadar I. Heavy metal content of flue-cured tobacco leaf in different growing regions of Hungary. Acta Agron Hung. 1993;43:243–51.Google Scholar
- 12.Rodgman A, Perfetti TA. The chemical components of tobacco and tobacco smoke. 2nd ed: Taylor and Francis Group; 2013.Google Scholar
- 13.Cadmium and cadmium compounds. Available at: https://monographs.iarc.fr/ENG/Monographs/vol100C/mono100C-8.pdf. Accessed 20 June 2018.
- 14.Development support document for cadmium and cadmium compounds. Texas Commission on Environmental Quality (TCEQ). 2016. Available at: http://www.tceq.texas.gov/assets/public/implementation/tox/dsd/final/cadmium.pdf. Accessed 26 March 2018.
- 19.Kapp R, Smoke T. In: Wexler P, Anderson BD, Peyster A, Gad SC, Hakkinen PJ, Kamrin MA, Locey BJ, Mehendale HM, Pope CN, Shugart LR, editors. Enclyclopedia of toxicology. 2nd ed: Elsevier; 2005. p. 200–2.Google Scholar
- 20.Baker RR, Chemistry S. In: Davis DL, Nielsen MT, editors. Tobacco production, chemistry and technology: Blackwell Science Ltd; 1999. p. 398–439.Google Scholar
- 21.John E, Coburn S, Liu C, McAughey J, Mariner D, McAdam KG, et al. Effect of temperature and humidity on the gas–particle partitioning of nicotine in mainstream cigarette smoke: a diffusion denuder study. J Aerosol Sci. 2018;117:100–17.Google Scholar
- 22.Williamson JT, Graham JF, Allman DR. The modification of cigarette smoke by filter tips. Beitr Tabakforsch. 1965;3:233–42.Google Scholar
- 24.Klus H, Boenke-Nimphius B, Muller L. Cigarette mainstream smoke: the evolution of method and devices for generation, exposure and collection. Beitr Tabakforsch. 2016;27:137–274.Google Scholar
- 25.Pacyna JM. Atmospheric emissions of arsenic, cadmium, lead and mercury from high temperature processes in power generation and industry. In: Hutchinson TC, Meema KM, editors. Lead, mercury, cadmium and arsenic in the environment: John Wiley & Sons Ltd; 1987. p. 69–87.Google Scholar
- 26.Breitinger DK. Cadmium and its inorganic compounds. In: Hermann WA, editor. Synthetic methods of organometallic and inorganic chemistry: Thieme; 1999. p. 167–81.Google Scholar
- 27.Roemer E, Schramke H, Weiler H, Buettner A, Kausche S, Weber S, et al. Mainstream smoke chemistry and in vitro and in vivo toxicity of the reference cigarettes 3R4F and 2R4F. Beitr Tabakforsch. 2012;25:316–35.Google Scholar
- 30.Ciftci H, Olcucu A. Determination of iron, copper, cadmium and zinc in some cigarette brands in Turkey. Int J Sci Technol. 2007;2:29–32.Google Scholar
- 31.IMEP-114: Determination of total Cd, Pb, As, Hg and Sn in feed premixes. Available at: http://publications.jrc.ec.europa.eu/repository/bitstream/JRC78163/jrc78163_imep-114%20full%20report.pdf. Accessed 20 June 2018.
- 32.Rodgman A, Perfetti TA. In: Rodgman A, Perfetti TA, editors. In the chemical components of tobacco and tobacco smoke. Boca Raton: Taylor and Francis Group, CRC Press; 2009.Google Scholar
- 36.Roemer E, Schramke H, Weiler H, Buettner A, Kausche S, Weber S, et al. Mainstream smoke chemistry and in vitro and in vivotoxicity of the reference cigarettes 3R4F and 2R4F. Beitr Tabakforsch Int. 2012;25:316–35.Google Scholar
- 37.Kuroki Y, Yokohama S, Takahashi H, Fujiwara M. Development of an analytical method for the simultaneous determination of trace metals and mercury in mainstream cigarette smoke by ICP-MS. 63rd Tobacco Science Research Conference 2009;63:49–50.Google Scholar
- 40.Nitsch A, Kalcher K, Greschonig H, Pietsch R. Schwermetalle in Tabaken und in Tabakrauchll: Spurenelemente Cadmium, Blei, Kupfer, Kobalt und Nickel in oesterreichischenZigaretten und derenRauchkondensaten und Rauchgasen. Beitr Tabakforsch Int. 1991;15:19–32.Google Scholar
- 42.Xue L, Thomas CE, Koller KB. Mainstream smoke gas phase filtration performance of adsorption materials evaluated with a puff-by-puff multiplex GC-MS method. Beitr Tabakforsch Int. 2002;20:251–6.Google Scholar
- 44.Alderman SL, Song C, Moldoveanu SC, Cole SK. Particle size distribution of e-cigarette aerosols and the relationship to Cambridge filter pad collection efficiency. Beitr Tabakforsch Int. 2014;26:183–90.Google Scholar
- 45.Techniques for the analysis of organic chemicals by inductively coupled plasma mass spectrometry (ICP-MS) Agilent Technologies Applications 5988-6190EN. Available at: http://www.youngin.com/application/AN-0809-0095EN.pdf. Accessed 26 March 2018.