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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: [email protected]
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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

References

Baddiel, C.B. and Berry, E.E. (1966) Spectra structure correlations in hydroxy and fluorapatite. Spectrochimica Ada, 22, 1407—1416.CrossRefGoogle Scholar
Basta, N.T., Gradwohl, R., Snethen, K.L. and Schroder, J.L. (2001) Chemical immobilization of lead, zinc and cadmium in smelter-contaminated soils using biosolids and rock phosphate. Journal of Environmental Quality, 30, 1222—1230.CrossRefGoogle ScholarPubMed
Bhatnagar, V.M. (1967) IR spectrum of strontium hydroxyapatite. Experimentia, 23, 697—699.CrossRefGoogle Scholar
Bhatnagar, V.M. (1968) IR spectra of hydroxyapatite and fluorapatite. Bulletine de la Societe Chimique France, 177 1—1773.Google Scholar
Bigi, A., Gandolfi, M., Gazzano, M., Ripamonti, A., Foresti, E. and Roveri, N. (1986) Thermal stability of cadmium-calcium hydroxylapatite solid solutions. Journal of the Chemical Society Dalton Transactions, 241—244.CrossRefGoogle Scholar
Bigi, A., Ripamonti, A., Bruckner, S., Gazzano, M., Roveri, N. and Thomas S.A. (1989) Structure refinements of lead-substituted calcium hydroxy-apatite by X-ray powder fitting. Ada Crystallographica, B45, 247—251.Google Scholar
Bigi, A., Gandolfi, M., Gazzano, M., Ripamonti, A., Roveri, N. and S.A., Thomas (1991) Structural modifications of hydroxyapatite induced by lead substitution for calcium. Journal of the Chemical Society Dalton Transactions, 2883—2886.CrossRefGoogle Scholar
Bigi, A., Falini, G., Gazzano, M., Roveri, N. and Tedesco, E. (1998) Structural refinements of strontium substituted hydroxyapatites. Material Science Forum, 278-281, 814—819.CrossRefGoogle Scholar
Binsted, N. (1998) EXCURV98. CCLRC Daresbury Laboratory, UK, Computer Program.Google Scholar
Cant, N.W., Bett, J.A.S., Wilson, GR. and Hall, W.K. (1971) The vibrational spectrum of hydroxyl groups in hydroxyapatites. Spectrochimica Ada, 27A, 425—439.CrossRefGoogle Scholar
Coffin, R.L. (1959) Strontium-calcium hydroxyapatite solid solutions: preparation and lattice constant measurements. Journal of the American Chemical Society, 81, 5275—5278.Google Scholar
Coffin, R.L. (1960) Strontium-calcium hydroxyapatite solid solutions precipitated from basic, aqueous solutions. Journal of the American Chemical Society, 82, 5067—5070.Google Scholar
Cotter-Howells, J. (1996) Lead phosphate formation in soils. Environmental Pollution, 93, 9—16.CrossRefGoogle ScholarPubMed
Cotter-Howells, J. and Caporn, S. (1996) Remediation of contaminated land by formation of heavy metal phosphates. Applied Geochemistry, 11, 335—342.CrossRefGoogle Scholar
Cotter-Howells, J., Champness, P.E., Charnock, J.M. and Pattrick, R.A.D. (1994) Identification of pyromorphite in mine-waste contaminated soils by ATEM and EXAFS. European Journal of Soil Science, 45, 393—402.CrossRefGoogle Scholar
Cressey, G., Batchelder, M. and Schofield, P.F. (1999) Rapid accurate phase quantification of contaminated soils and sediments. 1999 Winter Meeting of the Mineralogical Society of Great Britain & Ireland. Abstract.Google Scholar
Elliot, J.C. (1994) Structure and Chemistry of the Apatites and other Calcium Orthophosphates. Studies in Inorganic Chemistry, 18. Elsevier Science B.V., Amsterdam.Google Scholar
Griffith, W.P. (1970) Raman studies on rock-forming minerals. Part II. Minerals containing MO3, MO4, and MO6 groups. Journal of the Chemical Society (A), 286—291.CrossRefGoogle Scholar
Hata, M., Okada, K., Iwai, S., Ahao, M. and AoM, H. (1978) Cadmiumhydroxylapatite. Acta Crystallographica, B34, 3062—3064.CrossRefGoogle Scholar
Hettiarachchi, G.M., Pierzynski, GM. and Ransom, M.D. (2001) In situ stabilization of soil lead using phosphorus. Journal of Environmental Quality, 30, 1214—1221.CrossRefGoogle ScholarPubMed
Hodson, M.E., Valsami-Jones, E. and Cotter-Howells, J.D. (2000a Metal phosphates and remediation of contaminated land. Pp. 291—311: Environmental Mineralogy: Microbial Interactions, Anthropogenic Influences, Contaminated Land and Waste Management (Cotter-Howells, J.D., Campbell, L.S., Valsami-Jones, E. and Batchelder, M., editors). Special Series 9. Mineralogical Society of Great Britain & Ireland.Google Scholar
Hodson, M.E., Valsami-Jones, E. and Cotter-Howells, J.D. (2000b Bonemeal additions as a remediation treatment for metal contaminated soil. Environmental Science and Technology, 34, 3501—3507.CrossRefGoogle Scholar
Hughes, J.M., Cameron, M. and Crowley, K.D. (1991) Ordering of divalent cations in the apatite structure: Crystal structure refinements of natural Mn- and Sr-bearing apatite. American Mineralogist, 76, 1857—1862.Google Scholar
Jeanjean, J., Vincent, U. and Federoff, M. (1994) Structural modification of calcium hydroxyapatite induced by sorption of cadmium ions. Journal of Solid State Chemistry, 108, 68—72.CrossRefGoogle Scholar
Jeanjean, J., McGrellis, S., Rouchard, J.C., Federoff, M., Rondeau, A., Perocheau, S. and Dubis, A. (1996) A crystallographic study of the sorption of cadmium on calcium hydroxyapatites: Incidence of cation vacan¬cies. Journal of Solid State Chemistry, 126, 195—201.CrossRefGoogle Scholar
Laperche, V., Traina, S.J., Gaddam, P. and Logan, T.J. (1996) Chemical and mineralogical characterizations of Pb in a contaminated soil: Reactions with synthetic apatite. Environmental Science & Technology, 30, 3321—3326.CrossRefGoogle Scholar
Laperche, V., Logan, T.J., Gaddam, P. and Traina, S.J. (1997) Effect of apatite amendments on plant uptake of Pb from contaminated soil. Environmental Science & Technology, 31, 2747—2753.CrossRefGoogle Scholar
Larson, A.C. and Von Dreele, R.B. (1994) General Structure Analysis System (GSAS). Los Alamos National Laboratory Report LAUR 86-748 (revised version), New Mexico, USA, 223 pp.Google Scholar
Ma, Q.Y., Traina, S.J., Logan, T.J. and Ryan, J.A. (1993) In situ lead immobilization by apatite. Environmental Science and Technology, 27, 1803—1810.CrossRefGoogle Scholar
Ma, Q.Y., Logan, T.J., Traina, S.J. and Ryan, J.A. (1994) Effects of NO3¯, Cl¯, F¯, SO4¯ and CO3¯ on Pb2+ immobilization by hydroxyapatite. Environmental Science and Technology, 28, 408—418.CrossRefGoogle Scholar
Ma, Q.Y., Logan, T.J. and Traina, S.J. (1995) Lead immobilization from aqueous solutions and contami¬nated soils using phosphate rocks. Environmental Science and Technology, 29, 1118—1126.CrossRefGoogle Scholar
Manceau, A., Tamura, N., Marcus, M.A., MacDowell, A.A., Celeste, R.S., Sublett, R.E., Sposito, G. and Padmore, H.A. (2002) Deciphering nickel sequestra¬tion in soil ferromanganese nodules by combining X-ray fluorescence, absorption and diffraction at micrometer scales of resolution. American Mineralogist, 87, 1494—1499.CrossRefGoogle Scholar
Miyake, M., Ishigaki, K. and Suzuki, T. (1986) Structure refinements of Pb2+ ion-exchanged apatites by X-ray powder pattern fitting.. Journal of Solid State Chemistry, 61, 230—235.CrossRefGoogle Scholar
Morin, G., Ostergren, J.D., Juillot, D., Ildefonse, Ph., Calas, G. and Brown, G.E. (1999) XAFS determina¬tion of the chemical form of lead in smelter-contaminated soils and mine tailings: Importance of adsorption processes. American Mineralogist, 84, 420—434.CrossRefGoogle Scholar
Napper, D.H. and Smythe, B.M. (1966) The dissolution kinetics of hydroxyapatite in the presence of kink poisons. Journal of Dental Research, 45, 1775—1783.CrossRefGoogle ScholarPubMed
Narasaraju, T.S.B., Singh, R.P. and Rao, V.L.N. (1972) A new method of preparation of solid solutions of calcium and lead hydroxylapatites. Journal of Inorganic and Nuclear Chemistry, 34, 2072—2074.CrossRefGoogle Scholar
Nounah, A., Szlagyi, J. and Lacout, J.L. (1990) La substitution calcium-cadmium dans les hydroxyapa¬tites. Annales de Chimie-Science des Materiaux, 15, 409—419.Google Scholar
Nounah, A., Lacout, J.L. and Savariault, J.M. (1992) Localization of cadmium in cadmium-containing hydroxy- and fiuorapatites. Journal of Alloys and Compounds, 188, 141—146.CrossRefGoogle Scholar
Nriagu, J.O. (1984) Formation and stability of base metal phosphates in soils and sediments. Pp. 318—329 in: Phosphate Minerals (Nriagu, J.O. and Moore, P.B., editors). Springer-Verlag, London, UK.CrossRefGoogle Scholar
Pasteris, J.D., Wopenka, B., Freeman, J.J., Rogers, K., Valsami-Jones, E., van der Houwen, J.A.M. and Silva, M.J. (2004) Lack of OH in extremely nanocrystalline ‘hydroxylapatite’ : Implications for bone properties. Biomaterials, 25, 229—238.CrossRefGoogle Scholar
Sery, A., Manceau, A. and Greaves, G.N. (1996) Chemical state of Cd in apatite phosphate ores as determined by EXAFS spectroscopy. American Mineralogist, 81, 864—873.CrossRefGoogle Scholar
Ternane, R., Ferid, M., Trabelsi-Ayedi, M. and Piriou, B. (1999) Vibrational spectra of lead alkali apatites Pb8M2(PO4)6 with M = Ag and Na. Spectrochimica Ada Part A - Molecular And Biomolecular Spectroscopy, 55, 1793—1797.CrossRefGoogle Scholar
USEPA (1996) Proposed plan. Residential yard soil, Oronogo-Duenweg mining belt site, Jasper County, Missouri. US Environmental Protection Agency, Kansas City, Kansas, USA.Google Scholar
Valsami-Jones, E., Ragnarsdottir, K.V., Putnis, A., Bosbach, D., Kemp, A.J. and Cressey, G. (1998). The dissolution of apatite in the presence of aqueous metal cations at pH 2-7. Chemical Geology, 151, 215—233.CrossRefGoogle Scholar
Wood, P.A. (1997) Remediation methods for contami-nated sites. Pp. 47—71 in: Contaminated Land and its Reclamation (Hester, R.E. and Harrison, R.M., editors). Thomas Telford Publishing, London, UK.CrossRefGoogle Scholar