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Synchrotron X-ray absorption spectroscopy analysis of arsenic chemical speciation in human nail clippings

Ponomarenko, Olena ; Gherase, Mihai R. ; Leblanc, Mark S. ; Kim, Chang Yong ; Desouza, Elstan D. ; Farquharson, Michael J. ; McNeill, Fiona E. ; Nehzati, Susan LU ; Pickering, Ingrid J. and George, Graham N. , et al. (2014) In Environmental Chemistry 11(6). p.632-643
Abstract

Environmental context Chronic ingestion of arsenic leads to its accumulation in keratinous tissues, which can represent a risk factor for developing cancer. We use synchrotron X-ray absorption spectroscopy to investigate chemical bonding of arsenic in the keratins from nail clippings of volunteers from areas in Atlantic Canada with low-to-moderate arsenic contamination of drinking water. The study helps our understanding of arsenic metabolism and its role in cancer development. Abstract Drinking water aquifers in many areas of the world have naturally elevated levels of inorganic arsenic exceeding the World Health Organization limit. Arsenic concentrations in human nail clippings are commonly used as a biomarker of exposure to this... (More)

Environmental context Chronic ingestion of arsenic leads to its accumulation in keratinous tissues, which can represent a risk factor for developing cancer. We use synchrotron X-ray absorption spectroscopy to investigate chemical bonding of arsenic in the keratins from nail clippings of volunteers from areas in Atlantic Canada with low-to-moderate arsenic contamination of drinking water. The study helps our understanding of arsenic metabolism and its role in cancer development. Abstract Drinking water aquifers in many areas of the world have naturally elevated levels of inorganic arsenic exceeding the World Health Organization limit. Arsenic concentrations in human nail clippings are commonly used as a biomarker of exposure to this toxic element. However, the chemical form of arsenic accumulated in nail tissues is not well determined. We employed synchrotron microprobe and bulk X-ray absorption spectroscopy techniques to analyse the concentration and chemical speciation of arsenic in the finger- and toenail clippings of volunteers living in the vicinity of Sackville, New Brunswick, Canada. This area is known to have low-to-moderately elevated levels of arsenic in ground water. Arsenic species in clippings were represented by three main groups, distinguished by the As-K near-edge X-ray absorption fine structure spectra: (1) AsIII type, which can be fitted as a mixture of As bound to thiols, and also to oxygen or methyl groups, with a small contribution from AsV species, (2) AsV type, best represented by fitting arsenate in aqueous solution and (3) The AsIII+AsV mixture type. The high proportion (%) of sulfur-bound arsenic species most likely corresponds to binding between arsenic (in its trivalent and, to a lesser extent, pentavalent forms) and cysteine residues in the sulfur-rich fraction of keratin and keratin-associated proteins. Further work is needed to explore whether these chemical species could be used as toxicity biomarkers of human exposure to elevated levels of As in drinking water.

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publishing date
type
Contribution to journal
publication status
published
keywords
arsenicosis, chemical speciation, keratin, near-edge X-ray absorption fine structure, synchrotron X-ray fluorescence (XRF) imaging.
in
Environmental Chemistry
volume
11
issue
6
pages
12 pages
publisher
CSIRO Publishing
external identifiers
  • scopus:84918549985
ISSN
1448-2517
DOI
10.1071/EN13240
language
English
LU publication?
no
id
4f462768-bbfd-4bd5-9cd3-2ba851a54877
date added to LUP
2020-02-07 14:57:19
date last changed
2022-02-16 02:37:38
@article{4f462768-bbfd-4bd5-9cd3-2ba851a54877,
  abstract     = {{<p>Environmental context Chronic ingestion of arsenic leads to its accumulation in keratinous tissues, which can represent a risk factor for developing cancer. We use synchrotron X-ray absorption spectroscopy to investigate chemical bonding of arsenic in the keratins from nail clippings of volunteers from areas in Atlantic Canada with low-to-moderate arsenic contamination of drinking water. The study helps our understanding of arsenic metabolism and its role in cancer development. Abstract Drinking water aquifers in many areas of the world have naturally elevated levels of inorganic arsenic exceeding the World Health Organization limit. Arsenic concentrations in human nail clippings are commonly used as a biomarker of exposure to this toxic element. However, the chemical form of arsenic accumulated in nail tissues is not well determined. We employed synchrotron microprobe and bulk X-ray absorption spectroscopy techniques to analyse the concentration and chemical speciation of arsenic in the finger- and toenail clippings of volunteers living in the vicinity of Sackville, New Brunswick, Canada. This area is known to have low-to-moderately elevated levels of arsenic in ground water. Arsenic species in clippings were represented by three main groups, distinguished by the As-K near-edge X-ray absorption fine structure spectra: (1) AsIII type, which can be fitted as a mixture of As bound to thiols, and also to oxygen or methyl groups, with a small contribution from AsV species, (2) AsV type, best represented by fitting arsenate in aqueous solution and (3) The AsIII+AsV mixture type. The high proportion (%) of sulfur-bound arsenic species most likely corresponds to binding between arsenic (in its trivalent and, to a lesser extent, pentavalent forms) and cysteine residues in the sulfur-rich fraction of keratin and keratin-associated proteins. Further work is needed to explore whether these chemical species could be used as toxicity biomarkers of human exposure to elevated levels of As in drinking water.</p>}},
  author       = {{Ponomarenko, Olena and Gherase, Mihai R. and Leblanc, Mark S. and Kim, Chang Yong and Desouza, Elstan D. and Farquharson, Michael J. and McNeill, Fiona E. and Nehzati, Susan and Pickering, Ingrid J. and George, Graham N. and Fleming, David E.B.}},
  issn         = {{1448-2517}},
  keywords     = {{arsenicosis; chemical speciation; keratin; near-edge X-ray absorption fine structure; synchrotron X-ray fluorescence (XRF) imaging.}},
  language     = {{eng}},
  month        = {{01}},
  number       = {{6}},
  pages        = {{632--643}},
  publisher    = {{CSIRO Publishing}},
  series       = {{Environmental Chemistry}},
  title        = {{Synchrotron X-ray absorption spectroscopy analysis of arsenic chemical speciation in human nail clippings}},
  url          = {{http://dx.doi.org/10.1071/EN13240}},
  doi          = {{10.1071/EN13240}},
  volume       = {{11}},
  year         = {{2014}},
}