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The chemical form of mercury in fish - Response

Article  in  Science · September 2003


DOI: 10.1126/science.1085941 · Source: PubMed

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Hugh H Harris Ingrid Pickering


University of Adelaide University of Saskatchewan
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BREVIA
it remains intact in dilute aqueous solution
The Chemical Form (7 ). Methylmercury chloride is also fairly
hydrophobic and is thus expected to exhibit

of Mercury in Fish membrane-crossing properties superior to


other methylmercury species, which is ex-
pected to correlate with toxic properties
Hugh H. Harris,* Ingrid J. Pickering,† Graham N. George†‡ (1). The acidic high Cl– conditions in the
human stomach may convert methylmer-
cury cysteine species to the chloride, but
The primary dietary source of neurotoxic selenium-containing species, and the fish whether this occurs is, at present, unknown.
mercury compounds is via the ingestion of spectra closely resemble only the spectrum In at least one model system, methylmer-
methylmercury species accumulated in of methylmercury cysteine (or structurally cury cysteine proves to be much less toxic
fish. Methylmercury from fish has been related species), which contains linear than CH3HgCl; day-old zebrafish larvae
linked to neurological damage (Minamata two-coordinate mercury with methyl and tolerate 20-fold the concentration of meth-
disease) (1) and increased risk of myocar- cysteinyl sulfur donors. Thus, the near- ylmercury cysteine than CH3HgCl [sup-
dial infarction (2). Despite its importance, edge spectra indicate the coordination of porting online material (SOM) Text].
the complete chemical identity of the mer- the methylmercury in fish to be completed Considerable publicity has been given to
cury coordination in animal tissue remains by an aliphatic thiol. Although XAS cannot possible health hazards associated with
unknown. The toxic properties of any ele- eating fish, but ingestion of a mercury dose
ment are critically dependant on molecular through consumption of fish may have
form; for example, dialkylmercury deriva- quite different toxicological implica-
tives are toxic at such low levels that they tions than ingestion of the same mercu-
are considered supertoxic, whereas mercu- ry dose in the form of other methyl-
ric selenide has a relatively low toxicity mercury compounds.
and accumulates as an apparently benign
detoxification product in marine mammals
(3). Knowing the chemical nature of a po- References and Notes
1. R. A. Goyer et al., Toxicological Effects of Methylmer-
tential toxicant is, thus, essential to under- cury (National Academy Press, Washington, DC,
standing its toxic properties. Mercury is 2000).
2. M. D. Guallar et al., N. Engl. J. Med. 347, 1747
very flexible in its coordination of nonme- (2002).
tallic elements, with structurally character- 3. R. Wagemann, E. Trebacz, G. Boila, W. L. Lockhart, Sci.
ized species exhibiting coordination num- Total Environ. 218, 19 (1998).
bers between two and eight (4 ). X-ray 4. F. H. Allen, O. Kennard, Chem. Des. Autom. News 1,
31 (1993).
absorption spectroscopy (XAS) is ideally 5. Materials and methods are available as supporting
suited to identification of chemical forms in material on Science Online.
situ, but it previously has not been much 6. Solution species identity was confirmed by measur-
ing the extended x-ray absorption fine structure.
applied to molecular toxicology. Methylmercury cysteine showed Hg-C and Hg-S
Samples of fresh fish, otherwise intend- bond lengths of 2.06 and 2.35 Å, respectively.
ed for human consumption, were obtained 7. Aqueous CH3HgCl shows Hg-C and Hg-Cl bond-
lengths of 2.02 and 2.30 Å, respectively.
from a local fish market. The Hg LIII XAS 8. Research at the Stanford Synchrotron Radiation
(5) of three different fish—swordfish Laboratory was supported by DOE Office of Basic
(Xiphias gladius), orange roughy (Hop- Energy Services, Office of Biological and Environ-
Fig. 1. Comparison of the Hg LIII near-edge spec- mental Research, and by NIH National Center for
lostethus atlanticus), and sand sole (Pset- tra of swordfish with selected solution spectra. Research Resources. We thank Cook’s Seafood
tichthys melanostictus)—indicated Hg con- The points show the spectrum of the fish; the Market, Menlo Park, CA, for the gift of fresh fish
centrations within the range expected (6.0, solid lines show the spectra of aqueous solutions samples.
1.2, and 0.4 ␮M, respectively). The nor- of standard species, as follows: (A) CH3HgS(Cys),
Supporting Online Material
malized spectra of swordfish and orange (B) CH3HgCl, (C) Hg2⫹(Hg(NO3)2 solution), and www.sciencemag.org/cgi/content/full/301/5637/1203/
roughy were indistinguishable within the (D) Hg(SR)2, (E) [Hg(SR)4]2–. DC1
noise (sand sole was too “noisy” for com- Materials and Methods
SOM Text
parison), indicating similar or identical unambiguously identify the exact nature of
chemical forms of mercury. This is notable this thiol, cysteine is by a large margin the 21 April 2003; accepted 5 August 2003
given their different diets: orange roughy is most likely candidate as the predominant
midway in the food chain, feeding on crus- biological thiol, though it is likely part of a
taceans, small squid, and fish, whereas the larger peptide (e.g., glutathione) or protein. Stanford Synchrotron Radiation Laboratory, SLAC,
exclusively fish- and squid-eating sword- Our data have implications for the toxic MS 69, 2575 Sand Hill Road, Menlo Park, CA 94025,
fish is a top predator. properties expected from human consumption USA.
Figure 1 compares the Hg LIII x-ray of fish. The most commonly used “model” of *Present address: School of Chemistry, University of
absorption near-edge spectrum of sword- methylmercury species in fish is aqueous Sydney, NSW 2006, Australia.
fish skeletal muscle with the solution spec- methylmercury chloride (CH3HgCl), often er- †Present address: Department of Geological Sciences,
University of Saskatchewan, 114 Science Place, Saska-
tra of selected standard compounds (6 ). roneously referred to as CH3Hg⫹. The Hg-Cl toon, SK Canada S7N 5E2.
Twenty-six different standards were com- bond in methylmercury chloride is highly ‡To whom correspondence should be addressed. E-
pared overall, including glutathione- and covalent, and our measurements indicate that mail: g.george@stanford.edu

www.sciencemag.org SCIENCE VOL 301 29 AUGUST 2003 1203


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