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Speciation analysis in forensic science: Arsenic speciation is supporting the hypothesis that Napoleon was poisoned with inorganic arsenic

(29.07.2007)



Background

While it has been demonstrated already during the early 60`s by various analytical procedures (such as NAA) that high concentrations of arsenic were present in Napoleon`s hair, some authors challenged these results by indicating that the detected levels might be a result of external contamination. Different sources for external contamination were speculated including wallpaper, coal smoke, arsenic-containing cosmetics, or by arsenic used to preserve hair samples. Due to the geographical location of Saint Helena in the middle of the sea, it also has been speculated that arsenic in Napoleon's hair could be a result of seafood intake.

To continue active investigations, the ChemTox Laboratory at Illkirch, France was  requested by Dr. Ben Weider, President of the International Napoleonic Society (Montreal, Canada) to test two hair specimens derived from Napoleon for arsenic.


New results

Two strands of hair, referenced as Noverraz (cut on 6 May 1821) and Grand Maréchal Bertrand (cut on 6 May 1821.) were decontaminated from external arsenic by washing with acetone and then incubated 6 h in water at 90 °C. Arsenic speciation was carried out by HPLC–ICP/MS using a cation-exchange PRP-X200 column that allows the detection of arsenobetaine and an anion-exchange PRP-X100 column to test for the mineral forms.

The HPLC system was from SpectraSYSTEM (Thermo), consisting of a AS3000 autosampler and a P1000XR + SCM1000 pump. The column outlet in both cases was connected to the nebulizer of the ICP-MS (Thermo Electron X7).

In these conditions, the inorganic species As(III), As(V) and their metabolites (DMA and MMA) were separated. Analysis of hair samples highlighted massive amounts of total arsenic (42.1 and 37.4 ng/mg).

Arsenical species found in the two samples of analyzed hair are distributed in the following: As(III) 31.1 and 44.7%; As(V) 66.3 and 53.2%; DMA 0.42 and 0.15%. Traces of MMA were detected, and 2% of the species could not be identified.

Although arsenobetaine is poorly incorporated in hair, the absence of even traces of arsenobetaine indicates that seafood cannot account for the arsenic detected in Napoleon's hair. These results prove that more than 97% of the arsenic found in the hair of Napoleon is in inorganic form, which is consistent with a chronic intoxication by the most toxic inorganic arsenic species.


 The original study

Pascal Kintz, Morgane Ginet, Nadine Marques, Vincent Cirimele, Arsenic speciation of two specimens of Napoleon's hair, Forensic Sci. Int., 170/2-3 (2007) 204-206. doi:10.1016/j.forsciint.2007.02.035



Related studies

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H. Smith, S. Forshufud, A. Wassen, Distribution of arsenic in Napoléon's hair, Nature (London), 194 (1962) 725-726. doi:10.1038/194725a0

S. Forshufud, H. Smith, A. Wassen, Napoleon's illness 1816-1821 in the light of activation analyses in hairs from various dates, Arch. Toxicol.,  20 (1964) 210-219.   doi: 10.1007/BF00577893

H. Lander, P.R. Hodge, C.S. Crisp, Arsenic in hair and nails, its significance on acute arsenic poisoning, J. Forens. Med., 12 (1965) 52–67.

H.A. Shapiro, Arsenic content of human hair and nails, its interpretation, J. Forens. Med. 14 (1967) 65–71.

A.J. Van den Berg, J.J.M. de Geoij, J.P.W. Houtman, Arsenic Content of Human Hair After Washing as Determined by Activation Analysis, in:  J.R. DeVoe [ed.], Modern Trends in Activation Analysis, Vol. I. Washington, DC: NBS, 1968, pp. 272-282.

E.F. Pearson, C.A. Pounds, A case involving the administration of known amounts of arsenic, and its analysis in hair, J. Forens. Sci. Soc., 11 (1971) 229–234.

Rita Cornelis, Neutron activation analysis of hair, failure of a mission, J. Radioanal. Chem. 15 (1973) 305–316.

R.A. Smith, A method to distinguish between arsenic in, and on human hair,
Environ. Res. (U.S.A), 12 (1976) 171-173. doi:10.1016/0013-9351(76)90020-7

D. Maes, B.D. Pate, The absorption of arsenic into single human head hairs,
J. Forensic Sci., 22 (1977) 89-94.

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Arch. Toxicol., 41/2 (1978) 163-167. doi: 10.1007/BF00302528

D.E.H. Jones, K.W.D. Ledingham, Arsenic in Napoleon's wallpaper, Nature (London), 299 (1982) 626-627. doi:10.1038/299626a0

Peter K. Lewin, Ronald G.V. Hancock, Paul Voynovich, Napoleon Bonaparte: no evidence of chronic arsenic poisoning, Nature (London), 299 (1982) 627-628. doi:10.1038/299627a0

J.T. Hindmarsh, P.F. Corso, The death of Napoleon Bonaparte: a critical review of the cause, J. History Med., 53 (1998) 201-218.

B. Weider, J.H. Fournier, Activation analyses of authenticated hairs of Napoleon Bonaparte confirm arsenic poisoning, Am. J. Forensic Med. Pathol., 20/4 (1999) 378-382.

Amjad Shraim, Seishiro Hirano, Hiroshi Yamauchi, Extraction and Speciation of Arsenic in Hair Using HPLC-ICPMS, Anal. Sci., 17/Sup. (2001) 1729

S.J. Steindel, P.J. Howanitz, The uncertainty of hair analysis for trace metals, J. Am. Med. Assoc., 285 (2001) 83–85.

P. Kintz, J.P. Goullé, P. Fornes, B. Ludes, A new series of hair analyses from Napoleon confirms chronic exposure to arsenic, J. Anal. Toxicol., 26 (2002) 584-585.

T. Hindmarsh, P.F. Corso, Les cheveux de Napoléon, source externe ou ingestion d'arsenic ?, Ann. Toxicol. Anal., 14 (2002) 132

J. Thomas Hindmarsh, Caveats in hair analysis in chronic arsenic poisoning,
Clin. Biochem. (Ottawa), 35/1 (2002) 1-11. doi:10.1016/S0009-9120(01)00282-X

Xilei Lin, R. Henkelmann, Contents of arsenic, mercury and other trace elements in Napoleon's hair determined by INAA using the k0-method, J. Radioanal. Nucl. Chem., 257/3 (2003) 615-620.  doi: 10.1023/A:1026129319306

Xilei Lin, D. Alber, R. Henkelmann, Elemental contents in Napoleons hair cut before and after his death: did Napoleon die of arsenic poisoning ?, Anal. Bioanal. Chem., 379/2 (2004) 218-220. doi: 10.1007/s00216-004-2536-y

Francesco Mari, Elisabetta Bertol, Vittorio Fineschi, Steven B Karch, Channelling the Emperor: what really killed Napoleon?, Journal of The Royal Society of Medicine, 97/8 (2004) 397-399. DOI: 10.1258/0141076041550619

Jorge Yanez, Vladimir Fierro, Hector Mansilla, Leonardo Figueroa, Lorena Cornejo, Ramon M. Barnes, Arsenic speciation in human hair: a new perspective for epidemiological assessment in chronic arsenicism,  J. Environ. Monit., 7/12    (2005) 1335-1341. DOI: 10.1039/b506313b

Andrea Raab, Jörg Feldmann, Arsenic speciation in hair extracts, Anal. Bioanal. Chem., 381/2 (2005) 332-338. DOI: 10.1007/s00216-004-2796-6

Pascal Kintz, Morgane Ginet, Vincent Cirimele, Multi-Element Screening by ICP-MS of Two Specimens of Napoleon's Hair, J. Anal. Toxicol., 30/8 (2006) 621-623.

E. Sanz, R. Muñoz-Olivas, Christian Dietz, J. Sanz, Carmen Cámara, Alternative extraction methods for arsenic speciation in hair using ultrasound probe sonication and pressurised liquid extraction, J. Anal. At. Spectrom., 22/2 (2007) 131-139. DOI: 10.1039/b608064m



 Related information

 Wikipedia: Napoleon Bonaparte
Wikipedia: Arsenic poisoning
Wikipedia: Saint Helena
International Napoleonic Society: The assassination of Napoleon
International Napoleonic Society: The poisoning of Napoleon: The final proof
Napoleon Org: Arsenic and the Emperor
CrimeLibrary: The death of Napoleon, murder or natural causes ?
King James Medical Laboratory: Frequently Asked Question Regarding the Analysis of Metals in Hair Specimens
CDC/ATSDR: Hair Analysis: Exploring the State of the Science
EVISA: LC-ICP-MS: The most often used hyphenated system for speciation analysis



Related News

ABC News in science, June 6, 2001: Napoleon poisoning theory revived
NewScientistTech, October 29, 2002: Hair analysis clears Napoleon's 'poisoners'
Toxipedia. Napoleon's Death by Arsenic Exposure...?
Bryan Allison, Spring 2002: Cause of death: The mystery surrounding the death of Napoleon


last time modified: November 12, 2007









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