Insect excretes unusual six-coordinate pentavalent arsenic species
Ruwandi Andrahennadi A , Juxia Fu A , M. Jake Pushie A , Cheryl I. E. Wiramanaden A , Graham N. George A and Ingrid J. Pickering A BA Department of Geological Sciences, University of Saskatchewan, 114 Science Place, Saskatoon, SK, S7N 5E2, Canada.
B Corresponding author. Email: ingrid.pickering@usask.ca
Environmental Chemistry 6(4) 298-304 https://doi.org/10.1071/EN09029
Submitted: 6 March 2009 Accepted: 12 June 2009 Published: 25 August 2009
Environmental context. Arsenate, in which oxidised arsenic is coordinated to four oxygen atoms, is common in the environment. We have found that a moth larva excretes an unusual form of oxidised arsenic which is bound to six oxygen atoms. Since the chemical groups which give rise to this species are abundant in environmental and biological systems, more research is needed into the possible presence of such six-coordinate complexes in natural systems.
Abstract. Arsenate, in which pentavalent arsenic (AsV) is approximately tetrahedrally coordinated by oxygen, is common in biological or environmental systems. Octahedral coordination of AsV by oxygen is known chemically but hitherto has not been observed in natural systems. In an effort to understand the effect of elevated levels of arsenic on insects and other insectivorous animals in the food chain, larvae of the moth bertha armyworm (Mamestra configurata Walker) [Lepidoptera : Noctuidae] were examined under laboratory conditions. Synchrotron X-ray absorption spectroscopy was used to show that the exuvia (shed skin) and frass (fecal matter) contain an unusual AsV species six-coordinated by oxygen. The species is modelled as a low pH octahedral chelation complex with vicinal dihydroxyls such as glycerol or catechol. Structural characterisation using extended X-ray absorption fine structure (EXAFS) shows interatomic distances which are more similar to those of the glycerol complex and the near-edge also shows more similarity with the aliphatic chelator. The larvae may be using the six-coordinate AsV species as a specific excretory molecule. Since vicinal dihydroxyl species are common, more research is needed into the possible presence of such six-coordinate complexes in natural systems.
Acknowledgements
This research is supported by a Discovery Grant from the Natural Sciences and Engineering Research Council (NSERC) of Canada (to I. J. Pickering), the Canadian Institutes of Health Research (CIHR) and the Saskatchewan Health Research Foundation. I. J. Pickering and G. N. George are Canada Research Chairs. Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource (SSRL), a national user facility operated by Stanford University on behalf of the US Department of Energy, Office of Basic Energy Sciences. The SSRL Structural Molecular Biology Program is supported by the Department of Energy, Office of Biological and Environmental Research, and by the National Institutes of Health, National Center for Research Resources, Biomedical Technology Program. Part of this research was performed at the Canadian Light Source (CLS) which is supported by NSERC, the National Research Council (Canada), CIHR, and the University of Saskatchewan. We thank Agriculture and Agri-Food Canada (Saskatoon Research Centre) for insects and rearing facilities, Marlynn Mierau of the Department of Biology, University of Saskatchewan for bertha armyworm photography, Pickering and George group members for assistance with data collection and staff members at SSRL and CLS for their support.
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