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New Human Hair Reference Material Supporting the Biomonitoring of Methylmercury


Mercury is a global pollutant and classified by the World Health Organization as a major public health concern. Some inorganic mercury released to the environment is converted mainly by microorganisms into more toxic organic mercury. Organic mercury (methylmercury) is bioaccumulated in organisms and biomagnified in the food web. Humans are mainly exposed to methylmercury via consumption of seafood. Human biomonitoring is requested in order to evaluate actual exposure to the toxin. Hair is the preferred sample type for biomonitoring since it retains mercury well and its testing is non-invasive.

The main mercury species retained in the hair matrix is methylmercury. Certified reference materials (CRMs) for assessing mercury levels are required, as an increasing number of surveys are conducted to evaluate the effectiveness of regulations and policies driven by the Minamata Convention.

The new CRM:
Considering the demands of human biomonitoring of hair for mercury and other elements, the researchers developed a material with extended certification to cover some elements with toxicological and nutritional significance. To assure that the material is representative of human hair, contamination sources were minimized with great attention.

About 10 kg of scalp hair was collected from Vietnamese males in a barbershop in Hanoi. The hair was washed five times in a 0.3% neutral detergent, rinsed with tap water and finally with distilled water before drying at 60° overnight. The dried hair was pulverized by the combined action of a roll crusher, pin mill and air-jet mill to particles with a size below 74 µm. After rigorous blending, three gram aliquots of the homogenized hair powder were poured into borosilicate bottles and sterilized by gamma-irradiation.

An aliquot of 20 mg of the hair powder was sufficient to reach a standard deviation of less than 2.6 % for all certified elements.

The material was stable for the test period (12 months).

10 Laboratories provided results for methylmercury. Techniques used by the laboratories were GC-ECD (8 laboratories) and GC-AFS as well as HPLC-chemiluminescence. There was no bias between the techniques.  

Data for total mercury was provided by 19 laboratories. Techniques used were thermal decomposition-AAS (TD-AAS, 12 times), CV-AAS (4 times), CV-AFS (1 times) and ICP-QMS (3 times). The results obtained by ICP-MS were slightly higher than all others and were considered to be outliers and were excluded from the certification.

Results for the other elements were provided by 12 laboratories using ICP-QMS for determination. Unfortunately, the low number of acceptable results for arsenic did not allow for certification.

The following table compares the certified values for NIMD-1 with those of other Human hair CRMs.

 IAEA 086
 MeHg as Hg
 0.634 ± 0.071    3.8 ± 0.4  0.258 ± 0.021
 total Hg 
 0.794 ± 0.050
 4.42 ± 0.2  0.573 ± 0.039
 12.8 ± 1.4  15.3 ± 1.3 17.6 ± 0.9
 234 ± 29  172 ± 11  167 ± 7
 1.52 ± 0.29  1.79 ± 0.17 1.00 ± 0.20
 As (info)
 0.17 ± 0.03   0.10
* all values in mg/kg dry weight

The original study:

Koichi Haraguchi, Mineshi Sakamoto, Akito Matsuyama, Megumi Yamamoto, Dang T. Hung, Hiromitsu Nagasaka, Keisuke Uchida, Yasunori Ito, Hitoshi Kodamantani, Milena Horvat, Hing M. Chan, Matthew Rand, Ciprian M. Cirtiu, Byoung-Gwon Kim, Flemming Nielsen, Akane Yamakawa, Nikolay Mashyanov, Nikolai Panichev, Elena Panova, Tomoaki Watanabe, Naoki Kaneko, Jun Yoshinaga, Ranny F. Herwati, Alfrida E. Suoth, Hirokatsu Akagi, Development of Human Hair Reference Material Supporting the Biomonitoring of Methylmercury, Anal. Sci., 36/5 (2020) 561-567. DOI: 10.2116/analsci.19SBP07

Related studies (newest first)

Van Anh Thi Hoang, Hien Thu Thi Do, Tetsuro Agusa, Chihaya Koriyama, Suminori Akiba, Yasuhiro Ishibashi, Mineshi Sakamoto, Megumi Yamamoto, Hair mercury levels in relation to fish consumption among Vietnamese in Hanoi, J. Toxicol. Sci., 42/5 (2017) 651-662. DOI: 10.2131/jts.42.651

M. Esteban, B. K. Schindler, J. A. Jiménez, H. M. Koch, J. Angerer, M. Rosado, S. Gómez, L. Casteleyn, M. Kolossa-Gehring, K. Becker, L. Bloemen, G. Schoeters, E. Den Hond, O. Sepai, K. Exley, M. Horvat, L. E. Knudsen, A. Joas, R. Joas, D. Aerts, P. Biot, D. Borosová, F. Davidson, I. Dumitrascu, M. E. fischer, M. Grander, B. Janasik, K. Jones, L. Kašparová, T. Larssen, M. Naray, F. Nielsen, P. Hohenblum, R. Pinto, C. Pirard, G. Plateel, J. S. Tratnik, J. Wittsiepe, and A. Castańo, Mercury analysis in hair: Comparability and quality assessment within the transnational COPHES/DEMOCOPHES project, Environ Res., 141 (2015) 24-30. DOI: 10.1016/j.envres.2014.11.014

C. Ibanez-Palomino, J. F. López-Sánchez, and A. Sahuquillo, Certified reference materials for analytical mercury speciation in biological and environmental matrices: Do they meet user needs?; a review, Anal. Chim. Acta, 2012, 720, 9-15. DOI: 10.1016/j.aca.2012.01.015

K. Srogi, Mercury content of hair in different populations relative to fish consumption. Rev. Environ. Contam. Toxicol., 189 (2007) 107-130. DOI: 10.1007/978-0-387-35368-5_5

T. Agusa, T. Kunito, H. Iwata, I. Monirith, T.S. Tana, A. Subramanian, S. Tanabe, Mercury contamination in human hair and fish from Cambodia: levels, specific accumulation and risk assessment. Environ. Pollut., 134 (2005) 79-86. DOI: 10.1016/j.envpol.2004.07.015

M.A. McDowell, C.F. Dillon, J. Osterloh, P.M. Bolger, E.  Pellizzari, R. Fernando, R. Montes de Oca, S.E. Schober, T. Sinks, R.L. Jones, K.R. Mahaffey, Hair mercury levels in U.S. children and women of childbearing age: reference range data from NHANES 1999-2000. Environ. Health Perspect., 112 (2004) 1165-1171. DOI: 10.1289/ehp.7046 

J. Yoshinaga, M. Morita, K. Okamoto, New human hair certified reference material for methylmercury and trace elements, Fresenius J. Anal. Chem., 357 (1997) 279-283.
DOI:  10.1007/s002160050153

S.F. Stone, F.W. Backhaus, A.R. Byrne, S. Gangadharan, M. Horvat, K. Kratzer, R.M. Parr, J.D. Schladot, R. Zeisler, Production of hair intercomparison materials for use in population monitoring programmes for mercury and methylmercury exposure, Fresenius J. Anal. Chem., 1995, 352, 184-187. DOI: 10.1007/BF00322322.

K. Okamoto M. Morita, H. Quan, T. Uehiro, and K. Fuwa, Preparation and certification of human hair powder reference material, Clin. Chem., 1985, 31, 1592-1597. PMID: 4042324

 Related EVISA Resources

Material database: Human hair materials
Material database: CRMs with certified methyl mercury content


Related EVISA News

January 14, 2013: United Nations Global Mercury Treaty: Fifth and final session

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