RESEARCH PAPER
Consistency of arsenic speciation in global tobacco products with implications for health and regulation
 
More details
Hide details
1
Department of Earth & Environmental Sciences, University of St Andrews, St Andrews, UK
2
Institute for Global Food Security, Queen’s University Belfast, Belfast, UK
CORRESPONDING AUTHOR
W Edryd Stephens   

Department of Earth & Environmental Sciences, University of St Andrews, Irvine Building, North Street, St Andrews, Fife KY16 9AL, UK
Publish date: 2014-12-11
 
Tobacco Induced Diseases 2014;12(December):24
KEYWORDS
ABSTRACT
Background:
Tobacco smoke is a major risk to the health of its users and arsenic is among the components of smoke present at concentrations of toxicological concern. There are significant variations in human toxicity between inorganic and organic arsenic species and the aim of this study was to determine whether there are predictable relationships among major arsenic species in tobacco that could be useful for risk assessment.

Methods:
14 samples of tobacco were studied spanning a wide range of concentrations in samples from different geographical regions, including certified reference materials and cigarette products. Inorganic and major organic arsenic species were extracted from powdered tobacco samples by nitric acid using microwave digestion. Concentrations of arsenic species in these extracts were determined using HPLC-ICPMS.

Results:
The concentrations of total inorganic arsenic species range from 144 to 3914 μg kg-1, while organic species dimethylarsinic acid (DMA) ranges from 21 to 176 μg As kg-1, and monomethylarsonic acid (MA) ranges from 30 to 116 μg kg-1. The percentage of species eluted compared to the total arsenic extracted ranges from 11.1 to 36.8% suggesting that some As species (possibly macro-molecules, strongly complexed or in organic forms) do not elute from the column. This low percentage of column-speciated arsenic is indicative that more complex forms of arsenic exist in the tobacco. All the analysed species correlate positively with total arsenic concentration over the whole compositional range and regression analysis indicates a consistent ratio of about 4:1 in favour of inorganic arsenic compared with MA + DMA.

Conclusions:
The dominance of inorganic arsenic species among those components analysed is a marked feature of the diverse range of tobaccos selected for study. Such consistency is important in the context of a WHO expert panel recommendation to regulate tobacco crops and products using total arsenic concentration. If implemented more research would be required to develop models that accurately predict the smoker’s exposure to reduced inorganic arsenic species on the basis of leaf or product concentration and product design features.

 
REFERENCES (42)
1.
Talhout R, Schultz T, Florek E, van Benthem J, Wester P, Opperhuizen A: Hazardous compounds in tobacco smoke. Int J Environ Res Public Health. 2011, 8: 613-628. 10.3390/ijerph8020613.
 
2.
WHO: Report on the scientific basis of tobacco product regulation: fourth report of a WHO study group. Book Report on the Scientific Basis of Tobacco Product Regulation: Fourth Report of a WHO Study Group (Editor ed.^eds.). 2012, World Health Organisation, Geneva, Switzerland, 83.
 
3.
IARC: Arsenic, metals, fibres, and dusts. IARC monographs on the evaluation of carcinogenic risks to humans. Book Arsenic, Metals, Fibres, and Dusts. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans (Editor ed.^eds.). 2012, International Agency for Research on Cancer, Lyon, France, 501pp.
 
4.
Arsenic in drinking water. [http://www.who.int/water_sanit...].
 
5.
Lugon-Moulin N, Martin F, Krauss MR, Ramey PB, Rossi L: Arsenic concentration in tobacco leaves: a study on three commercially important tobacco (nicotiana tabacum L.) types. Water Air Soil Pollut. 2008, 192: 315-319. 10.1007/s11270-008-9658-3.
 
6.
Behera SN, Xian H, Balasubramanian R: Human health risk associated with exposure to toxic elements in mainstream and sidestream cigarette smoke. Sci Total Environ. 2014, 472: 947-956. 10.1016/j.scitotenv.2013.11.063.
 
7.
Counts ME, Morton MJ, Laffoon SW, Cox RH, Lipowicz PJ: Smoke composition and predicting relationships for international commercial cigarettes smoked with three machine-smoking conditions. Regul Toxicol Pharmacol. 2005, 41: 185-227. 10.1016/j.yrtph.2004.12.002.
 
8.
Gregg E, Hill C, Hollywood M, Kearney M, McAdam K, McLaughlin D, Purkis S, Williams M: The UK smoke constituents testing study: Summary of results and comparison with other studies. Beiträge zur Tabakforschung International. 2004, 21: 117-138.
 
9.
Pappas S, Fresquez MR, Martone N, Watson CH: Toxic metal concentrations in mainstream smoke from cigarettes available in the USA. J Anal Toxicol. 2014, 38: 204-211. 10.1093/jat/bku013.
 
10.
Campbell RCJ, Stephens WE, Finch AA, Geraki K: Controls on the valence species of arsenic in tobacco smoke: XANES investigation with implications for health and regulation. Environ Sci Technol. 2014, 6: 3449-3456. 10.1021/es4039243.
 
11.
Liu C, Wright CG, McAdam KG, Taebunpakul S, Heroult J, Braybrook J, Goenaga-Infante H: Arsenic speciation in tobacco and cigarette smoke. Beiträge zur Tabakforschung Int Contrib Tob Res. 2012, 25: 375-380.
 
12.
Taebunpakul S, Liu C, Wright C, McAdam K, Heroult J, Braybrook J, Goenaga-Infante H: Determination of total arsenic and arsenic speciation in tobacco products: from tobacco leaf and cigarette smoke. J Anal At Spectrom. 2011, 26: 1633-1640. 10.1039/c0ja00268b.
 
13.
Zhang J, Liu X, Huang C, Liu Z, Xu H, Xie W: Speciation analysis of arsenic in tobacco and tobacco products. Tob Sci Tech. 2013, 6: 53-56.
 
14.
Stephens WE, Calder A, Newton J: Source and health implications of high toxic metal concentrations in illicit tobacco products. Environ Sci Tech. 2005, 39 (2): 479-488. 10.1021/es049038s.
 
15.
Dybczynski R, Polkowskamotrenko H, Samczynski Z, Szopa Z: New polish certified reference materials for multielement inorganic trace analysis. Fresenius J Anal Chem. 1993, 345: 99-103. 10.1007/BF00322563.
 
16.
Dybczynski R, Polkowskamotrenko H, Samczynski Z, Szopa Z: Virginia tobacco leaves (CTA-VTL-2) - New polish CRM for inorganic trace analysis including microanalysis. Fresenius J Anal Chem. 1998, 360: 384-387. 10.1007/s002160050718.
 
17.
Stephens WE, Calder A: Analysis of non-organic elements in plant foliage using polarised X-ray fluorescence spectrometry. Anal Chim Acta. 2004, 527: 89-96. 10.1016/j.aca.2004.08.015.
 
18.
Yuping W, Dongdan W, Qiongzhen L, Jinhui Y: Determination of some metal elements from the HCl lixivium of tobacco by inductively coupled plasma-atomic emission spectrometry. Chin J Anal Chem. 2002, 30: 315-317.
 
19.
Chepiga TA, Morton MJ, Murphy PA, Avalos JT, Bombick BR, Doolittle DJ, Borgerding MF, Swauger JE: A comparison of the mainstream smoke chemistry and mutagenicity of a representative sample of the US cigarette market with two Kentucky reference cigarettes (K1R4F and K1R5F). Food Chem Toxicol. 2000, 38: 949-962. 10.1016/S0278-6915(00)00086-7.
 
20.
Dombovari J, Becker JS, Dietze HJ: Multielemental analysis in small amounts of environmental reference materials with inductively coupled plasma mass spectrometry. Fresenius J Anal Chem. 2000, 367: 407-413. 10.1007/s002160000378.
 
21.
Meharg AA, Deacon C, Campbell RCJ, Carey AM, Williams PN, Feldmann J, Raab A: Inorganic arsenic levels in rice milk exceed EU and US drinking water standards. J Environ Monit. 2008, 10: 428-431. 10.1039/b800981c.
 
22.
Williams PN, Price AH, Raab A, Hossain SA, Feldmann J, Meharg AA: Variation in arsenic speciation and concentration in paddy rice related to dietary exposure. Environ Sci Technol. 2005, 39: 5531-5540. 10.1021/es0502324.
 
23.
Williams PN, Villada A, Deacon C, Raab A, Figuerola J, Green AJ, Feldmann J, Meharg AA: Greatly enhanced arsenic shoot assimilation in rice leads to elevated grain levels compared to wheat and barley. Environ Sci Technol. 2007, 41: 6854-6859. 10.1021/es070627i.
 
24.
Francesconi KA, Kuehnelt D: Determination of arsenic species: A critical review of methods and applications, 2000-2003. Analyst. 2004, 129: 373-395. 10.1039/b401321m.
 
25.
Templeton DM, Ariese F, Cornelis R, Danielsson LG, Muntau H, Van Leeuwen HP, Lobinski R: Guidelines for terms related to chemical speciation and fractionation of elements. Definitions, structural aspects, and methodological approaches (IUPAC Recommendations 2000). Pure Appl Chem. 2000, 72: 1453-1470. 10.1351/pac200072081453.
 
26.
Raab A, Williams PN, Meharg AA, Feldmann J: Uptake and translocation of inorganic and methylated arsenic species by plants. Environ Chem. 2007, 4: 197-203. 10.1071/EN06079.
 
27.
Raab A, Baskaran C, Feldmann J, Meharg AA: Cooking rice in a high water to rice ratio reduces inorganic arsenic content. J Environ Monit. 2009, 11: 41-44. 10.1039/b816906c.
 
28.
Raber G, Stock N, Hanel P, Murko M, Navratilova J, Francesconi KA: An improved HPLC-ICPMS method for determining inorganic arsenic in food: application to rice, wheat and tuna fish. Food Chem. 2012, 134: 524-532. 10.1016/j.foodchem.2012.02.113.
 
29.
Abedin MJ, Cresser MS, Meharg AA, Feldmann J, Cotter-Howells J: Arsenic accumulation and metabolism in rice (Oryza sativa L.). Environ Sci Technol. 2002, 36: 962-968. 10.1021/es0101678.
 
30.
Hansen HR, Raab A, Price AH, Duan GL, Zhu YG, Norton GJ, Feldmann J, Meharg AA: Identification of tetramethylarsonium in rice grains with elevated arsenic content. J Environ Monit. 2011, 13: 32-34. 10.1039/c0em00460j.
 
31.
Saito A, Higuchi K, Hirai M, Nakane R, Yoshiba M, Tadano T: Selection and characterization of a nickel-tolerant cell line from tobacco (Nicotiana tabacum cv. bright yellow-2) suspension culture. Physiol Plant. 2005, 125: 441-453.
 
32.
Lomax C, Liu WJ, Wu LY, Xue K, Xiong JB, Zhou JZ, McGrath SP, Meharg AA, Miller AJ, Zhao FJ: Methylated arsenic species in plants originate from soil microorganisms. New Phytol. 2012, 193: 665-672. 10.1111/j.1469-8137.2011.03956.x.
 
33.
Bolan NS, Duraisamy VP: Role of inorganic and organic soil amendments on immobilisation and phytoavailability of heavy metals: a review involving specific case studies. Aust J Soil Res. 2003, 41: 533-555. 10.1071/SR02122.
 
34.
Kalcher K, Kern W, Pietsch R: Cadmium and lead in the smoke of a filter cigarette. Sci Total Environ. 1993, 128: 21-35. 10.1016/0048-9697(93)90177-8.
 
35.
Fowles J, Dybing E: Application of toxicological risk assessment principles to the chemical constituents of cigarette smoke. Tob Control. 2003, 12: 424-436. 10.1136/tc.12.4.424.
 
36.
Laugesen M, Fowles J: Scope for regulation of cigarette smoke toxicity according to brand differences in toxicant emissions. New Zeal Med J. 2005, 118: 1401-1414.
 
37.
Eriksen M, Mackay J, Ross H: The Tobacco Atlas. 2012, American Cancer Society & American Lung Foundation, Atlanta, Georgia, USA, 4.
 
38.
Fresquez MR, Pappas RS, Watson CH: Establishment of toxic metal reference range in tobacco from US cigarettes. J Anal Toxicol. 2013, 37: 298-304. 10.1093/jat/bkt021.
 
39.
O’Connor RJ, Li Q, Stephens WE, Hammond D, Elton-Marshall T, Cummings KM, Giovino GA, Fong GT: Cigarettes sold in China: design, emissions and metals. Tob Control. 2010, 19: 47-53. 10.1136/tc.2009.030163.
 
40.
Smoking: How to save a billion lives. [http://www.economist.com/node/...].
 
41.
Rodgman A, Perfetti TA: The Chemical Components of Tobacco and Tobacco Smoke. 2008, CRC Press, Boca Raton, Florida, USA.
 
42.
Stephens WE: Dependence of tar, nicotine and carbon monoxide yields on physical parameters: implications for exposure, emissions control and monitoring. Tob Control. 2007, 16: 170-176. 10.1136/tc.2006.017491.
 
 
CITATIONS (9):
1.
Inorganic arsenic inhibits the nucleotide excision repair pathway and reduces the expression of XPC
Nathaniel Holcomb, Mamta Goswami, Sung Gu Han, Tim Scott, John D’Orazio, David K. Orren, C. Gary Gairola, Isabel Mellon
DNA Repair
 
2.
Association of arsenic exposure with smoking, alcohol, and caffeine consumption: Data from NHANES 2005–2010
Ram B. Jain
Environmental Toxicology and Pharmacology
 
3.
Arsenic Speciation and Cadmium Determination in Tobacco Leaves, Ash and Smoke
Takahiro IWAI, Koichi CHIBA, Tomohiro NARUKAWA
Analytical Sciences
 
4.
Atomic Spectrometry Update: review of advances in elemental speciation
Robert Clough, Chris F. Harrington, Steve J. Hill, Yolanda Madrid, Julian F. Tyson
Journal of Analytical Atomic Spectrometry
 
5.
Estimation of Total and Inorganic Arsenic Intake from the Diet in Korean Adults
Mi-Na Seo, Seul-Gi Lee, Sang-Yong Eom, Jeongseon Kim, Se-Young Oh, Ho-Jang Kwon, Heon Kim, Byung-Sun Choi, Il-Je Yu, Jung-Duck Park
Archives of Environmental Contamination and Toxicology
 
6.
Levels of heavy metals in the raw and processed Ethiopian tobacco leaves
Girma Regassa, Bhagwan Singh Chandravanshi
SpringerPlus
 
7.
Complementary HPLC-ICP-MS and synchrotron X-ray absorption spectroscopy for speciation analysis of chromium in tobacco samples
Susana Cuello, John Entwisle, Jocelyn Benning, Chuan Liu, Steven Coburn, Kevin G. McAdam, Julian Braybrook, Heidi Goenaga-Infante
Journal of Analytical Atomic Spectrometry
 
8.
Comparing the cancer potencies of emissions from vapourised nicotine products including e-cigarettes with those of tobacco smoke
William E Stephens
Tobacco Control
 
9.
Redox metabolism of ingested arsenic: Integrated activities of microbiome and host on toxicological outcomes
Barbara A. Roggenbeck, Elaine M. Leslie, Seth T. Walk, Edward E. Schmidt
Current Opinion in Toxicology
 
eISSN:1617-9625