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Characterization and identification of mixed-metal phosphates in soils: the application of Raman spectroscopy

Published online by Cambridge University Press:  05 July 2018

A. M. Lanfranco ,
P. F. Schofield ,
P. J. Murphy ,
M. E. Hodson ,
J. F. W. Mosselmans  and
E. Valsami-Jones
A. M. Lanfranco
Affiliation:
Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD, UK
P. F. Schofield*
Affiliation:
Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD, UK
P. J. Murphy
Affiliation:
School of Earth Sciences and Geography, Kingston University, Kingston upon Thames, Surrey KT1 2EE, UK
M. E. Hodson
Affiliation:
Department of Soil Science, School of Human and Environmental Sciences, The University of Reading, Whiteknights, Reading RG6 6DW, UK
J. F. W. Mosselmans
Affiliation:
CLRC Daresbury Laboratory, Daresbury, Warrington WA4 4AD, UK
E. Valsami-Jones
Affiliation:
Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD, UK
*
* E-mail: pfs@nhm.ac.uk
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Abstract

The development of protocols for the identification of metal phosphates in phosphate-treated, metalcontaminated soils is a necessary yet problematical step in the validation of remediation schemes involving immobilization of metals as phosphate phases. The potential for Raman spectroscopy to be applied to the identification of these phosphates in soils has yet to be fully explored. With this in mind, a range of synthetic mixed-metal hydroxylapatites has been characterized and added to soils at known concentrations for analysis using both bulk X-ray powder diffraction (XRD) and Raman spectroscopy.

Mixed-metal hydroxylapatites in the binary series Ca –Cd, Ca –Pb, Ca –Sr and Cd –Pb synthesized in the presence of acetate and carbonate ions, were characterized using a range of analytical techniques including XRD, analytical scanning electron microscopy (SEM), infrared spectroscopy (IR), inductively coupled plasma-atomic emission spectrometry (ICP-AES) and Raman spectroscopy. Only the Ca –Cd series displays complete solid solution, although under the synthesis conditions of this study the Cd5(PO4)3OH end member could not be synthesized as a pure phase. Within the Ca –Cd series the cell parameters, IR active modes and Raman active bands vary linearly as a function of Cd content. X-ray diffraction and extended X-ray absorption fine structure spectroscopy (EXAFS) suggest that the Cd is distributed across both the Ca(1) and Ca(2) sites, even at low Cd concentrations.

In order to explore the likely detection limits for mixed-metal phosphates in soils for XRD and Raman spectroscopy, soils doped with mixed-metal hydroxylapatites at concentrations of 5, 1 and 0.5 wt.% were then studied. X-ray diffraction could not confirm unambiguously the presence or identity of mixed-metal phosphates in soils at concentrations below 5 wt.%. Raman spectroscopy proved a far more sensitive method for the identification of mixed-metal hydroxylapatites in soils, which could positively identify the presence of such phases in soils at all the dopant concentrations used in this study. Moreover, Raman spectroscopy could also provide an accurate assessment of the degree of chemical substitution in the hydroxylapatites even when present in soils at concentrations as low as 0.1%.

Keywords

mixed-metal phosphatesRaman spectroscopyXRD
Type
Research Article
Information
Mineralogical Magazine , Volume 67 , Issue 6 , December 2003 , pp. 1299 - 1316
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2003

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Footnotes

†

Current address: Corso Trapani 137, I-10141, Torino, Italy

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