Rethinking the Minamata Tragedy: What Mercury Species Was Really Responsible?

James, Ashley K.; Nehzati, Susan; Dolgova, Natalia V.; Sokaras, Dimosthenis; Kroll, Thomas; Eto, Komyo; O’Donoghue, John L.; Watson, Gene E.; Myers, Gary J.; Krone, Patrick H.; Pickering, Ingrid J.; George, Graham N.

doi:10.1021/acs.est.9b06253

Rethinking the Minamata Tragedy: What Mercury Species Was Really Responsible?

Journal Article · Fri Jan 17 00:00:00 EST 2020 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.9b06253· OSTI ID:1608345

James, Ashley K. ^[1]; Nehzati, Susan ^[1]; Dolgova, Natalia V. ^[1]; Sokaras, Dimosthenis ^[2]; Kroll, Thomas ^[2]; Eto, Komyo ^[3]; O’Donoghue, John L. ^[4]; Watson, Gene E. ^[4]; Myers, Gary J. ^[4]; Krone, Patrick H. ^[1]; ^[1]; ^[1]

Univ. of Saskatchewan, Saskatoon, SK (Canada)
SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Ministry of the Environment, Kumamoto (Japan). National Inst. for Minamata Disease
Univ. of Rochester, NY (United States)

Industrial release of mercury into the local Minamata environment with consequent poisoning of local communities through contaminated fish and shellfish consumption is considered the classic case of environmental mercury poisoning. However, the mercury species in the factory effluent has proved controversial, originally suggested as inorganic, and more recently as methylmercury species. In this investigation, we used newly available methods to re-examine the cerebellum of historic Cat 717, which was fed factory effluent mixed with food to confirm the source. Synchrotron high-energy-resolution fluorescence detection-X-ray absorption spectroscopy revealed sulfur-bound organometallic mercury with a minor β-HgS phase. Density functional theory indicated energetic preference for α-mercuri-acetaldehyde as a waste product of aldehyde production. The consequences of this alternative species in the “classic” mercury poisoning should be re-evaluated.

View Accepted Manuscript (DOE)

Research Organization:: SLAC National Accelerator Laboratory, Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: Canada Foundation for Innovation (CFI); Canada Research Chairs; National Institute of General Medical Sciences (NIGMS); National Institutes of Health (NIH); Natural Sciences and Engineering Research Council of Canada (NSERC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)

Grant/Contract Number:: AC02-76SF00515

OSTI ID:: 1608345

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 5 Vol. 54; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (43)

Inorganic mercury von Burg, R. Journal of Applied Toxicology, Vol. 15, Issue 6 https://doi.org/10.1002/jat.2550150610	journal	November 1995
A pathological study of Minamata disease in Japan Takeuchi, T.; Morikawa, N.; Matsumoto, H. Acta Neuropathologica, Vol. 2, Issue 1 https://doi.org/10.1007/BF00685743	journal	January 1962
X-ray absorption spectroscopy of selenium-containing amino acids Pickering, I. J.; George, Graham N.; Van Fleet-Stalder, Verena JBIC Journal of Biological Inorganic Chemistry, Vol. 4, Issue 6 https://doi.org/10.1007/s007750050352	journal	December 1999
Importance of Molar Ratios in Selenium-Dependent Protection Against Methylmercury Toxicity Ralston, Nicholas V. C.; Blackwell, J. Lloyd; Raymond, Laura J. Biological Trace Element Research, Vol. 119, Issue 3 https://doi.org/10.1007/s12011-007-8005-7	journal	July 2007
Mercuretin as the condensation polymer of tris(acetoxymercuri)acetic acid. The crystal structure of (ClHg)3CCOOH · DMSO Grdenić, D.; Korpar-Čolig, B.; Sikirica, M. Journal of Organometallic Chemistry, Vol. 276, Issue 1 https://doi.org/10.1016/0022-328X(84)80598-7	journal	November 1984
Monomercurated acetic acid. The crystal structure of NO3HgCH2COOH Grdenić, D.; Korpar-Čolig, B.; Matković-Čalogović, D. Journal of Organometallic Chemistry, Vol. 411, Issue 1-2 https://doi.org/10.1016/0022-328X(91)86002-8	journal	July 1991
Synthesis, spectroscopic, and X-say structural characterization of methylmercury-? , ? -selenocysteinate monohydrate, a key model for the methylmercury(II)-selenoprotein interaction Carty, A. Journal of Inorganic Biochemistry, Vol. 18, Issue 4 https://doi.org/10.1016/0162-0134(83)85044-2	journal	July 1983
A 13-element Ge detector for fluorescence EXAFS Cramer, S. P.; Tench, O.; Yocum, M. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 266, Issue 1-3 https://doi.org/10.1016/0168-9002(88)90449-4	journal	April 1988
Sulfur K-edge X-ray absorption spectroscopy for determining the chemical speciation of sulfur in biological systems Pickering, Ingrid J.; Prince, Roger C.; Divers, Thomas FEBS Letters, Vol. 441, Issue 1 https://doi.org/10.1016/S0014-5793(98)01402-1	journal	December 1998
Compilation of x-ray cross sections UCRL-50174, sections I, II revision 1, III, IV McMaster, W. H.; Kerr Del Grande, N.; Mallett, J. H. Atomic Data and Nuclear Data Tables, Vol. 8, Issue 4-6 https://doi.org/10.1016/S0092-640X(70)80026-2	journal	December 1970
X-ray spectroscopy and imaging of selenium in living systems Dolgova, Natalia V.; Nehzati, Susan; Choudhury, Sanjukta Biochimica et Biophysica Acta (BBA) - General Subjects, Vol. 1862, Issue 11 https://doi.org/10.1016/j.bbagen.2018.04.024	journal	November 2018
Arsenic–selenium and mercury–selenium bonds in biology Gailer, J. Coordination Chemistry Reviews, Vol. 251, Issue 1-2 https://doi.org/10.1016/j.ccr.2006.07.018	journal	January 2007
Molecular interaction between mercury and selenium in neurotoxicity Bjørklund, Geir; Aaseth, Jan; Ajsuvakova, Olga P. Coordination Chemistry Reviews, Vol. 332 https://doi.org/10.1016/j.ccr.2016.10.009	journal	February 2017
A Photochemically Generated Selenyl Free Radical Observed by High Energy Resolution Fluorescence Detected X-ray Absorption Spectroscopy Nehzati, Susan; Dolgova, Natalia V.; Sokaras, Dimosthenis Inorganic Chemistry, Vol. 57, Issue 17 https://doi.org/10.1021/acs.inorgchem.8b01522	journal	August 2018
The Chemical Nature of Mercury in Human Brain Following Poisoning or Environmental Exposure Korbas, Malgorzata; O’Donoghue, John L.; Watson, Gene E. ACS Chemical Neuroscience, Vol. 1, Issue 12 https://doi.org/10.1021/cn1000765	journal	October 2010
Critical Review. The effect of environmental pollutants on human reproduction, including birth defects Kurzel, Richard B.; Cetrulo, Curtis L. Environmental Science & Technology, Vol. 15, Issue 6 https://doi.org/10.1021/es00088a001	journal	June 1981
A distorted mercury [Hg(SR)4]2- complex with alkanethiolate ligands: the fictile coordination sphere of monomeric [Hg(SR)x] complexes Govindaswamy, Nandakumar; Moy, Jayson; Millar, Michelle Inorganic Chemistry, Vol. 31, Issue 26 https://doi.org/10.1021/ic00052a001	journal	December 1992
Degradation Mechanism of Methyl Mercury Selenoamino Acid Complexes: A Computational Study Asaduzzaman, Abu Md.; Schreckenbach, Georg Inorganic Chemistry, Vol. 50, Issue 6 https://doi.org/10.1021/ic1021406	journal	March 2011
Acetaldehyde by the Chisso Process Othmer, D. F.; Kon, Kichiro.; Igarashi, Takeo. Industrial & Engineering Chemistry, Vol. 48, Issue 8 https://doi.org/10.1021/ie50560a024	journal	August 1956
Theoretical x-ray absorption fine structure standards Rehr, J. J.; Mustre de Leon, J.; Zabinsky, S. I. Journal of the American Chemical Society, Vol. 113, Issue 14 https://doi.org/10.1021/ja00014a001	journal	July 1991
The Molybdenum Site of Sulfite Oxidase: A Comparison of Wild-Type and the Cysteine 207 to Serine Mutant Using X-ray Absorption Spectroscopy George, Graham N.; Garrett, Robert M.; Prince, Roger C. Journal of the American Chemical Society, Vol. 118, Issue 36 https://doi.org/10.1021/ja961218h	journal	January 1996
M11-L: A Local Density Functional That Provides Improved Accuracy for Electronic Structure Calculations in Chemistry and Physics Peverati, Roberto; Truhlar, Donald G. The Journal of Physical Chemistry Letters, Vol. 3, Issue 1 https://doi.org/10.1021/jz201525m	journal	December 2011
Structural Basis of the Antagonism between Inorganic Mercury and Selenium in Mammals Gailer, Jürgen; George, Graham N.; Pickering, Ingrid J. Chemical Research in Toxicology, Vol. 13, Issue 11 https://doi.org/10.1021/tx000050h	journal	November 2000
Molecular Mimicry in Mercury Toxicology Hoffmeyer, Ruth E.; Singh, Satya P.; Doonan, Christian J. Chemical Research in Toxicology, Vol. 19, Issue 6 https://doi.org/10.1021/tx0503449	journal	June 2006
Chemical Demethylation of Methylmercury by Selenoamino Acids Khan, Mohammad A. K.; Wang, Feiyue Chemical Research in Toxicology, Vol. 23, Issue 7 https://doi.org/10.1021/tx100080s	journal	July 2010
Interaction of mercury and selenium in the larval stage zebrafish vertebrate model MacDonald, Tracy C.; Korbas, Malgorzata; James, Ashley K. Metallomics, Vol. 7, Issue 8 https://doi.org/10.1039/C5MT00145E	journal	January 2015
Disruption of selenium transport and function is a major contributor to mercury toxicity in zebrafish larvae Dolgova, Natalia V.; Nehzati, Susan; MacDonald, Tracy C. Metallomics, Vol. 11, Issue 3 https://doi.org/10.1039/C8MT00315G	journal	January 2019
Chemical alterations to murine brain tissue induced by formalin fixation: implications for biospectroscopic imaging and mapping studies of disease pathogenesis Hackett, Mark J.; McQuillan, James A.; El-Assaad, Fatima The Analyst, Vol. 136, Issue 14 https://doi.org/10.1039/c0an00269k	journal	January 2011
From molecules to solids with the DMol3 approach Delley, B. The Journal of Chemical Physics, Vol. 113, Issue 18 https://doi.org/10.1063/1.1316015	journal	November 2000
An all‐electron numerical method for solving the local density functional for polyatomic molecules Delley, B. The Journal of Chemical Physics, Vol. 92, Issue 1 https://doi.org/10.1063/1.458452	journal	January 1990
A seven-crystal Johann-type hard x-ray spectrometer at the Stanford Synchrotron Radiation Lightsource Sokaras, D.; Weng, T. -C.; Nordlund, D. Review of Scientific Instruments, Vol. 84, Issue 5 https://doi.org/10.1063/1.4803669	journal	May 2013
Methylmercury Poisoning in Common Marmosets—A Study of Selective Vulnerability Within the Cerebral Cortex Eto, Komyo; Yasutake, Akira; Kuwana, Takashi Toxicologic Pathology, Vol. 29, Issue 5 https://doi.org/10.1080/019262301317226375	journal	August 2001
The Toxicology of Mercury and Its Chemical Compounds Clarkson, Thomas W.; Magos, Laszlo Critical Reviews in Toxicology, Vol. 36, Issue 8 https://doi.org/10.1080/10408440600845619	journal	January 2006
Ab initio curved-wave x-ray-absorption fine structure Mustre de Leon, J.; Rehr, J. J.; Zabinsky, S. I. Physical Review B, Vol. 44, Issue 9 https://doi.org/10.1103/PhysRevB.44.4146	journal	September 1991
Structure of (chloromercurio)acetaldehyde Halfpenny, J.; Small, R. W. H. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 35, Issue 5 https://doi.org/10.1107/S056774087900604X	journal	May 1979
XAS-Collect : a computer program for X-ray absorption spectroscopic data acquisition George, Martin J. Journal of Synchrotron Radiation, Vol. 7, Issue 4 https://doi.org/10.1107/S090904950000683X	journal	July 2000
The pathology of methylmercury poisoning (Minamata disease): The 50th Anniversary of Japanese Society of Neuropathology Eto, Komyo; Marumoto, Masumi; Takeya, Motohiro Neuropathology https://doi.org/10.1111/j.1440-1789.2010.01119.x	journal	June 2010
Focal Cerebral and Cerebellar Atrophy in a Human Subject due to Organic Mercury Compounds Hunter, D.; Russell, D. S. Journal of Neurology, Neurosurgery & Psychiatry, Vol. 17, Issue 4 https://doi.org/10.1136/jnnp.17.4.235	journal	November 1954
Congenital Minamata Disease: Warnings From Japan's Experience Kondo, Kiyotaro Journal of Child Neurology, Vol. 15, Issue 7 https://doi.org/10.1177/088307380001500707	journal	July 2000
Formaldehyde fixation. Fox, C. H.; Johnson, F. B.; Whiting, J. Journal of Histochemistry & Cytochemistry, Vol. 33, Issue 8 https://doi.org/10.1177/33.8.3894502	journal	August 1985
The crystal-structures of the sulphides of mercury Buckley, H. E.; Vernon, W. S. Mineralogical Magazine and Journal of the Mineralogical Society, Vol. 20, Issue 110 https://doi.org/10.1180/minmag.1925.020.110.02	journal	September 1925
XIX. Röntgenographische Untersuchungen an natürlichem und synthetischem Metacinnabarit (HgS). Lehmann, W. M. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 60, Issue 1-6 https://doi.org/10.1524/zkri.1924.60.1.379	journal	November 1924
Reappraisal of the Historic 1959 Cat Experiment in Minamata by the Chisso Factory. Eto, Komyo; Yasutake, Akira; Nakano, Atsuhiro The Tohoku Journal of Experimental Medicine, Vol. 194, Issue 4 https://doi.org/10.1620/tjem.194.197	journal	January 2001

Similar Records

Mercury pollution perspective

Journal Article · Sat Dec 31 23:00:00 EST 1977 · Water Spectrum; (United States) · OSTI ID:5589898

Volatilization of mercury compounds by methylmercury-volatilizing bacteria in Minamata Bay sediment

Journal Article · Mon Oct 31 23:00:00 EST 1988 · Bull. Environ. Contam. Toxicol.; (United States) · OSTI ID:6148864

Expansion of methylmercury poisoning outside of Minamata: An epidemiological study on chronic methylmercury poisoning outside of Minamata

Journal Article · Sat Jul 01 00:00:00 EDT 1995 · Environmental Research · OSTI ID:443495

Related Subjects

54 ENVIRONMENTAL SCIENCES
Alkyls
Cat 717
Central nervous system
Extended X-ray absorption fine structure
Manufacturing
Mercury

Rethinking the Minamata Tragedy: What Mercury Species Was Really Responsible?

Citation Formats

References (43)

Similar Records

Related Subjects