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Article << Previous     |         Contents Vol 11(3)

Speciation mapping of environmental samples using XANES imaging

Barbara E. Etschmann A B, Erica Donner C D, Joël Brugger E, Daryl L. Howard F, Martin D. de Jonge F, David Paterson F, Ravi Naidu C D, Kirk G. Scheckel G, Chris G. Ryan H and Enzo Lombi C I

A Mineralogy, South Australian Museum, North Terrace, Adelaide, GPO Box 234, SA 5001, Australia.
B School of Chemical Engineering, University of Adelaide, North Terrace, Adelaide, SA 5005, Australia.
C Centre for Environmental Risk Assessment and Remediation, University of South Australia, Building X, Mawson Lakes Campus, SA 5095, Australia.
D CRC CARE, PO Box 486, Salisbury, SA 5106, Australia.
E School of Geosciences, Monash University, Building 28, Clayton, Vic. 3800, Australia
F Australian Synchrotron, 800 Blackburn Road, Clayton, Vic. 3168, Australia
G US Environmental Protection Agency, Office of Research and Development, 5995 Center Hill Avenue, Cincinnati, OH 45224-1702, USA.
H Earth Science and Resource Engineering, Commonwealth Scientific and Industrial Research Organisation (CSIRO), Bayview Avenue, Clayton, Vic. 3168, Australia.
I Corresponding author: enzo.lombi@unisa.edu.au

Environmental Chemistry 11(3) 341-350 http://dx.doi.org/10.1071/EN13189
Submitted: 15 October 2013  Accepted: 28 February 2014   Published: 5 June 2014

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Environmental context. Recently developed fast fluorescence detectors have opened the way to the development of element speciation mapping, i.e. X-ray absorption near edge spectroscopy (XANES) imaging, of environmental samples. This technique is potentially very informative but is also highly data intensive. Here, we used XANES imaging to explore the distribution of Cu species in biosolid materials, destined for agricultural use, as this is of importance in relation to the bioavailability and potential toxicity of this metal.

Abstract. Fast X-ray detectors with large solid angles and high dynamic ranges open the door to XANES imaging, in which millions of spectra are collected to image the speciation of metals at micrometre resolution, over areas up to several square centimetres. This paper explores how such multispectral datasets can be analysed in order to provide further insights into the distribution of Cu species in fresh and stockpiled biosolids. The approach demonstrated uses Principal Components Analysis to extract the ‘significant’ spectral information from the XANES maps, followed by cluster analysis to locate regions of contrasting spectral signatures. Following this model-free analysis, pixel-by-pixel linear combination fits are used to provide a direct link between bulk and imaging XANES spectroscopy. The results indicate that both the speciation and distribution of Cu species are significantly affected by ageing. The majority of heterogeneously distributed micrometre-sized Cu sulfide particles present in fresh biosolids disappear during the oxidative stockpiling process. In aged biosolids most of the Cu is homogeneously redistributed on organic matter suggesting that Cu mobility is temporarily increased during this redistribution process. This manuscript demonstrates how large XANES imaging datasets could be analysed and used to gain a deep understanding of metal speciation in environmental samples.

Additional keywords: agriculture, biosolids, copper.


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