Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Assessment of arsenic species in human hair, toenail and urine and their association with water and staple food


Arsenic intake from household drinking/cooking water and food may represent a significant exposure pathway to induce cancer and non-cancer health effects. This study is based on the human biomonitoring of 395 volunteers from 223 households with private water sources located in rural Punjab, Pakistan. This work has shown the relative contribution of water and staple food to arsenic intake and accumulation by multiple biological matrix measurements of inorganic and organic arsenic species, while accounting for potential confounders such as age, gender, occupation, and exposure duration of the study population. Multi-variable linear regression showed a strong significant relationship between total arsenic (tAs) intake from water and concentrations of tAs, inorganic arsenic (iAs), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA) in urine and toenail samples. tAs intake from staple food (rice and wheat) also showed a strong significant relationship with hair tAs and iAs. The sole impact of staple food intake on biomarkers was assessed and a significant correlation was found with all of the urinary arsenic metabolites. Toenail was found to be the most valuable biomarker of past exposure to inorganic and organic arsenic species of dietary and metabolic origin.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.


  1. 1.

    Cottingham KL, Karimi R, Gruber JF, Zens MS, Sayarath V, Folt CL, et al. Diet and toenail arsenic concentrations in a New Hampshire population with arsenic-containing water. Nutr J. 2013;12:149.

    Article  Google Scholar 

  2. 2.

    International Agency for Research on Cancer. Arsenic, Metals, Fibres and Dusts, 2012.IARC Monographs on the Evaluation of Carcinogenic Risks to Humans.Lyon, France: IARC Working Group.pp.1-112.volume 1.

  3. 3.

    Aposhian HV, Aposhian MM. Arsenic toxicology: five questions. Chem Res Toxicol. 2006;19:1–15.

    CAS  Article  Google Scholar 

  4. 4.

    Orloff K, Mistry K, Metcalf S. Biomonitoring for environmental exposures to arsenic. J Toxicol Environ Health B Crit Rev. 2009;12:509–24.

    CAS  Article  Google Scholar 

  5. 5.

    Agency for Toxic Substances and Disease Registry. Toxicological profile for arsenic. Atlanta, GA: U.S. Department of Health and Human Services, 2007.

    Google Scholar 

  6. 6.

    Raab A, Feldmann J. Arsenic speciation in hair extracts. Anal Bioanal Chem. 2005;381:332–8.

    CAS  Article  Google Scholar 

  7. 7.

    Hinwood AL, Sim MR, Jolley D, de Klerk N, Bastone EB, Gerostamoulos J, et al. Hair and toenail arsenic concentrations of residents living in areas with high environmental arsenic concentrations. Environ Health Perspect. 2003;111:187–93.

    CAS  Article  Google Scholar 

  8. 8.

    Fleckman P, Allan C. Surgical anatomy of the nail unit. Dermatologic Surgery. 2001;27:257–60.

    CAS  Google Scholar 

  9. 9.

    Garland M, Morris JS, Rosner BA, Stampfer MJ, Spate VL, Baskett CJ, et al. Toenail trace element levels as biomarkers: reproducibility over a 6-year period. Cancer epidemiology, biomarkers & prevention: a publication of the American Association for Cancer Research, cosponsored by the American Society of Preventive. Oncology. 1993;2:493–7.

    CAS  Google Scholar 

  10. 10.

    European Food Safety Authority. Dietary exposure to inorganic arsenic in the European population. EFSA Journal. 2014;12:3597.

  11. 11.

    Ahsan H, Chen Y, Parvez F, Zablotska L, Argos M, Hussain I, et al. Arsenic exposure from drinking water and risk of premalignant skin lesions in Bangladesh: baseline results from the Health Effects of Arsenic Longitudinal Study. Am J Epidemiol. 2006;163:1138–48.

    Article  Google Scholar 

  12. 12.

    Lindberg AL, Rahman M, Persson LA, Vahter M. The risk of arsenic induced skin lesions in Bangladeshi men and women is affected by arsenic metabolism and the age at first exposure. Toxicol Appl Pharmacol. 2008;230:9–16.

    CAS  Article  Google Scholar 

  13. 13.

    Shen H, Niu Q, Xu M, Rui D, Xu S, Feng G, et al. Factors affecting arsenic methylation in arsenic-exposed humans: a systematic review and meta-analysis. Int J Environ Res Public Health. 2016;13:205.

    Article  Google Scholar 

  14. 14.

    Tsuji JS, Benson R, Schoof RA, Hook GC. Health effect levels for risk assessment of childhood exposure to arsenic. Regul Toxicol Pharmacol. 2004;39:99–110.

    CAS  Article  Google Scholar 

  15. 15.

    Rasheed H, Kay P, Slack R, Gong YY, Carter A. Human exposure assessment of different arsenic species in household water sources in a high risk arsenic area. Sci Total Environ. 2017;584-585:631–41.

    CAS  Article  Google Scholar 

  16. 16.

    Rasheed H, Slack R, Kay P, Gong YY. Refinement of arsenic attributable health risks in rural Pakistan using population specific dietary intake values. Environ Int. 2017;99 (Supplement C):331–42.

    Article  Google Scholar 

  17. 17.

    American Industrial Hygiene Association. Biological Monitoring: A Practical Field Manual. United States of America, 2004. February 27, 2004.AIHA Guideline 1—2004.pp 1-112. ISBN: 1-931504-51–2.

  18. 18.

    Bonsnes RW, Taussky HH. On the colorimetric determination of creatinine by the jaffe reaction. J Biol Chem. 1945;158:581–91.

    CAS  Google Scholar 

  19. 19.

    Hata A, Endo Y, Nakajima Y, Ikebe M, Ogawa M, Fujitani N, et al. HPLC-ICP-MS speciation analysis of arsenic in urine of Japanese subjects without occupational exposure. J Occup Health. 2007;49:217–23.

    CAS  Article  Google Scholar 

  20. 20.

    Middleton DR, Watts MJ, Hamilton EM, Fletcher T, Leonardi GS, Close RM, et al. Prolonged exposure to arsenic in UK private water supplies: toenail, hair and drinking water concentrations. Environ Sci Process & Impacts. 2016;18:562–74.

    CAS  Article  Google Scholar 

  21. 21.

    Button M, Jenkin GR, Harrington CF, Watts MJ. Human toenails as a biomarker of exposure to elevated environmental arsenic. J Environ Monit: Jem. 2009;11:610–7.

    CAS  Article  Google Scholar 

  22. 22.

    United States Environmental Protection Agency. EPA Method 3050B: Acid Digestion of Sediments, Sludges, and Soils, 1996.Revision 2. Washington, DC.

  23. 23.

    World Health Organization. Guidelines for drinking-water quality. 1996.Volume 2: Health Criteria and Other Supporting Information Second edition 1996. pp.1–973. ISBN 92 4 154480 5.

  24. 24.

    Melak D, Ferreccio C, Kalman D, Parra R, Acevedo J, Pérez L, et al. Arsenic Methylation and Lung and Bladder Cancer in a Case-control Study in Northern Chile. Toxicol Appl Pharmacol. 2014;274:225–31.

    CAS  Article  Google Scholar 

  25. 25.

    Middleton DR, Watts MJ, Hamilton EM, Ander EL, Close RM, Exley KS, et al. Urinary arsenic profiles reveal exposures to inorganic arsenic from private drinking water supplies in Cornwall, UK. Sci Rep. 2016;6:25656.

    CAS  Article  Google Scholar 

  26. 26.

    Zhang Q, Li Y, Liu J, Wang D, Zheng Q, Sun G. Differences of urinary arsenic metabolites and methylation capacity between individuals with and without skin lesions in inner Mongolia, Northern China. Int J Environ Res Public Health. 2014;11:7319–32.

    CAS  Article  Google Scholar 

  27. 27.

    Nizam S, Kato M, Yatsuya H, Khalequzzaman M, Ohnuma S, Naito H, et al. Differences in urinary arsenic metabolites between diabetic and non-diabetic subjects in Bangladesh. Int J Environ Res Public Health. 2013;10:1006–19.

    CAS  Article  Google Scholar 

  28. 28.

    Vahter ME. Interactions between arsenic-induced toxicity and nutrition in early life. J Nutr. 2007;137:2798–804.

    CAS  Article  Google Scholar 

  29. 29.

    Grashow R, Zhang J, Fang SC, Weisskopf MG, Christiani DC, Cavallari JM. Toenail metal concentration as a biomarker of occupational welding fume exposure. J Occup Environ Hyg. 2014;11:397–405.

    CAS  Article  Google Scholar 

  30. 30.

    Normandin L, Ayotte P, Levallois P, Ibanez Y, Courteau M, Kennedy G, et al. Biomarkers of arsenic exposure and effects in a Canadian rural population exposed through groundwater consumption. J Expo Sci Environ Epidemiol. 2014;24:127–34.

    CAS  Article  Google Scholar 

  31. 31.

    Rivera-Nunez Z, Meliker JR, Meeker JD, Slotnick MJ, Nriagu JO. Urinary arsenic species, toenail arsenic, and arsenic intake estimates in a Michigan population with low levels of arsenic in drinking water. J Expo Sci Environ Epidemiol. 2012;22:182–90.

    CAS  Article  Google Scholar 

  32. 32.

    Beane Freeman LE, Dennis LK, Lynch CF, Thorne PS, Just CL. Toenail arsenic content and cutaneous melanoma in Iowa. Am J Epidemiol. 2004;160:679–87.

    Article  Google Scholar 

  33. 33.

    Heck JE, Andrew AS, Onega T, Rigas JR, Jackson BP, Karagas MR, et al. Lung Cancer in a U.S. population with low to moderate arsenic exposure. Environ Health Perspect. 2009;117:1718–23.

    CAS  Article  Google Scholar 

  34. 34.

    RASHEED, H., KAY, P., SLACK, R. & GONG, Y. Y. 2018. Arsenic species in wheat, raw and cooked rice: Exposure and associated health implications. Science of The Total Environment, 634 pp. 366–373.

Download references


HR is grateful to the Schlumberger faculty for future fellowship, which enabled her to conduct field work and academic research as part of her PhD. We extend our thanks for the laboratory analysis support provided by the Brooks Applied Laboratory, USA.

Author information



Corresponding author

Correspondence to Hifza Rasheed.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Rasheed, H., Kay, P., Slack, R. et al. Assessment of arsenic species in human hair, toenail and urine and their association with water and staple food. J Expo Sci Environ Epidemiol 29, 624–632 (2019).

Download citation


  • Monomethylarsonic acid
  • Dimethylarsonic acid
  • Toenail arsenic
  • Dietary exposure
  • Urinary arsenic metabolites

Further reading


Quick links