THE VIBRATIONAL SPECTROSCOPY OF MINERALS WAYDE NEIL MARTENS B. APPL. SCI. (APPL. CHEM.) M.SC. (APPL. SCI.) Inorganic Materials Research Program, School of Physical and Chemical Science, Queensland University of Technology A THESIS SUBMITED FOR THE DEGREE OF DOCTOR OF PHILOSOPHY OF THE QUEENSLAND UNIVERSITY OF TECHNOLOGY 2004 2 Toss another rock on the Raman… 3 KEYWORDS Annabergite Aragonite Arupite Baricite Cerussite Erythrite Hörnesite Infrared Spectroscopy Köttigite Minerals Parasymplesite Raman Spectroscopy Solid Solutions Strontianite Vibrational Spectroscopy Vivianite Witherite 4 ABSTRACT This thesis focuses on the vibrational spectroscopy of the aragonite and vivianite arsenate minerals (erythrite, annabergite and hörnesite), specifically the assignment of the spectra. The infrared and Raman spectra of cerussite have been assigned according to the vibrational symmetry species. The assignment of satellite bands to 18O isotopes has been discussed with respect to the use of these bands to the quantification of the isotopes. Overtone and combination bands have been assigned according to symmetry species and their corresponding fundamental vibrations. The vibrational spectra of cerussite have been compared with other aragonite group minerals and the differences explained on the basis of differing chemistry and crystal structures of these minerals. The single crystal spectra of natural erythrite has been reported and compared with the synthetic equivalent. The symmetry species of the vibrations have been assigned according to single crystal and factor group considerations. Deuteration experiments have allowed the assignment of water vibrational frequencies to discrete water molecules in the crystal structure. Differences in the spectra of other vivianite arsenates, namely annabergite and hörnesite, have been explained by consideration of their differing chemistry and crystal structures. A novel approach to the assignment of site occupancy of ions in the erythrite – annabergite solid solution has been reported. This approach has utilised vibrational spectroscopy, in conjunction with careful consideration of the crystal structures of the minerals. It has been shown that in the erythrite – annabergite solid solution Co 5 prefers metal site 2 contrasting nickel which prefers site 1. This study in conjunction with other studies has yielded the trend that the more electronegative metal prefers to occupy site 1, with the least electronegative metal preferring to occupy site 2. Fundamentally this thesis has increased the knowledge base of the spectroscopic properties of the aragonite and the vivianite minerals. The site occupancy of metal ion substitutions in solid solution series of the vivianite group of minerals has been further enhanced, with novel method of studying the site occupancy of ions in solid solutions has been developed. A detailed knowledge and understanding of factor group analysis applied to the study of minerals has been achieved. 6 PUBLICATIONS WRITTEN IN THE COURSE OF STUDY 1. Martens, W., N., Rintoul, L., Kloprogge, J.T., and Frost, R., L. (2004) Raman single crystal study of cerussite. American Mineralogist, 89, 352-358. 2. Martens, W., N., Kloprogge, J.T., Frost, R., L., and Rintoul, L. (2004) Site occupancy of Co and Ni in erythrite - annabergite solid solutions by vibrational spectroscopy. American Mineralogist, Submitted. 3. Martens, W., N., Kloprogge, J.T., Frost, R., L., and Rintoul, L.. (2004) Single-crystal Raman study of erythrite,Co3(AsO4)2·8H2O. Journal of Raman Spectroscopy, 35, 208-216. 4. Martens, W.N., Frost, R.L., and Williams, P.A. (2003) The basic copper phosphate minerals pseudomalachite, ludjibaite and reichenbachite: An infrared emission and Raman spectroscopic study. Neues Jahrbuch fuer Mineralogie, Monatshefte(8), 337-362. 5. Martens, W.N., Frost, R.L., Kloprogge, J.T., and Williams, P.A. (2003) The basic copper arsenate minerals olivenite, cornubite, cornwallite, and clinoclase: An infrared emission and Raman spectroscopic study. American Mineralogist, 88(4), 501-508. 6. Martens, W., Frost, R.L., and Williams, P.A. (2003) Molecular structure of the adelite group of minerals - a Raman spectroscopic study. Journal of Raman Spectroscopy, 34(2), 104-111. 7. Martens, W., Frost, R.L., and Williams, P.A.. (2003) Raman and infrared spectroscopic study of the basic copper chloride minerals - implications for the study of the copper and brass corrosion and "bronze disease". Neues Jahrbuch fuer Mineralogie, Abhandlungen, 178(2), 197-215. 8. Martens, W., Frost, R.L., Kloprogge, J.T., and Williams, P.A. (2003) Raman spectroscopic study of the basic copper sulphates-implications for copper corrosion and "bronze disease". Journal of Raman Spectroscopy, 34(2), 145- 151. 9. Martens, W., Frost, R.L., and Kloprogge, J.T. (2003) Raman spectroscopy of synthetic erythrite, partially dehydrated erythrite and hydrothermally synthesized dehydrated erythrite. Journal of Raman Spectroscopy, 34(1), 90- 95. 10. Martens, W., and Frost, R.L. (2003) An infrared spectroscopic study of the basic copper phosphate minerals: Cornetite, libethenite, and pseudomalachite. American Mineralogist, 88(1), 37-46. 11. Martens, W.N., Frost, R.L., Kristof, J., and Kloprogge, J.T. (2002) Raman spectroscopy of dimethyl sulphoxide and deuterated dimethyl sulphoxide at 298 and 77 K. Journal of Raman Spectroscopy, 33(2), 84-91. 7 12. Martens, W.N., Frost, R.L., Kristof, J., and Horvath, E. (2002) Modification of Kaolinite Surfaces through Intercalation with Deuterated Dimethylsulfoxide. Journal of Physical Chemistry B, 106(16), 4162-4171. 13. Martens, W.N., Ding, Z., Frost, R.L., Kristof, J., and Kloprogge, J.T. (2002) Raman spectroscopy of hydrazine-intercalated kaolinite at 77, 298, 323, 343 and 358 K. Journal of Raman Spectroscopy, 33(1), 31-36. 14. Martens, W.N., Kloprogge, J.T., Frost, R.L., and Bartlett, J.R. (2002) A Crystallite Packing Model for Pseudoboehmite Formed during the Hydrolysis of Trisecbutoxyaluminium to Explain the Peptizability. Journal of Colloid and Interface Science, 247(1), 132-137. 15. Kristof, J., Frost, R.L., Martens, W.N., and Horvath, E. (2002) Separation of Adsorbed and Intercalated Hydrazine in Hydrazine-Hydrate Intercalated Kaolinite by Controlled-Rate Thermal Analysis. Langmuir, 18(4), 1244-1249. 16. Kloprogge, J.T., Visser, D., Martens, W.N., Duong, L.V., and Frost, R.L. (2003) Identification by RAMAN microscopy of magnesian vivianite formed 2+ 2+ 2+ 3- from Fe , Mg , Mn and PO4 in a Roman camp near fort Vechten, Utrecht, The Netherlands. Netherlands Journal of Geosciences, 82(2), 209-214. 17. Kloprogge, J.T., Martens, W.N., Nothdurft, L., Duong, L.V., and Webb, G.E. (2003) Low temperature synthesis and characterization of nesquehonite. Journal of Materials Science Letters, 22(11), 825-829. 18. Kloprogge, J.T., Hickey, L., Doung, L.V., Martens, W., N., and Frost, R., L. (2004) Synthesis and characterization of K2Ca5(SO4)6·H2O, the equivalent of görgeyite, a rare evaporite mineral. American Mineralogist, 89, 266-272. 19. Johnson, T.E., Martens, W., Frost, R.L., Ding, Z., and Kloprogge, J.T. (2002) Structured water in hydrotalcites of formula MgxZn6-xAl2(OH)16(CO3).4H2O: a Raman microscopic study. Journal of Raman Spectroscopy, 33(8), 604-609. 20. Frost, R.L., Williams, P.A., Martens, W., Kloprogge, J.T., and Leverett, P. (2002) Raman spectroscopy of the basic copper phosphate minerals cornetite, libethenite, pseudomalachite, reichenbachite and ludjibaite. Journal of Raman Spectroscopy, 33(4), 260-263. 21. Frost, R.L., Williams, P.A., Martens, W., and Kloprogge, J.T. (2002) Raman spectroscopy of the polyanionic copper(II) minerals buttgenbachite and connellite: implications for studies of ancient copper objects and bronzes. Journal of Raman Spectroscopy, 33(9), 752-757. 22. Frost, R.L., Williams, P.A., and Martens, W. (2003) Raman spectroscopy of the minerals boleite, cumengeite, diaboleite and phosgenite - implications for the analysis of cosmetics of antiquity. Mineralogical Magazine, 67(1), 103- 111. 8 23. Frost, R.L., Williams, P.A., Kloprogge, J.T., and Martens, W. (2003) Raman spectroscopy of the copper chloride minerals nantokite, eriochalcite and claringbullite - implications for copper corrosion. Neues Jahrbuch fuer Mineralogie, Monatshefte(10), 433-445. 24. Frost, R.L., Weier, M.L., Martens, W., Kloprogge, J.T., and Ding, Z. (2003) Dehydration of synthetic and natural vivianite. Thermochimica Acta, 401(2), 121-130. 25. Frost, R.L., Weier, M.L., Martens, W., Kloprogge, J.T., and Ding, Z.. (2003) Thermal decomposition of the vivianite arsenates-implications for soil remediation. Thermochimica Acta, 403(2), 237-249. 26. Frost, R.L., Martens, W.N., and Williams, P.A. (2002) Raman spectroscopy of the phase-related basic copper arsenate minerals olivenite, cornwallite, cornubite and clinoclase. Journal of Raman Spectroscopy, 33(5), 475-484. 27. Frost, R.L., Martens, W.N., Rintoul, L., Mahmutagic, E., and Kloprogge, J.T. (2002) Raman spectroscopic study of azurite and malachite at 298 and 77 K. Journal of Raman Spectroscopy, 33(4), 252-259. 28. Frost, R.L., Martens, W.N., Kloprogge, T., and Williams, P.A. (2002) Vibrational spectroscopy of the basic manganese and ferric phosphate minerals: Strunzite, ferrostrunzite and ferristrunzite. Neues Jahrbuch fuer Mineralogie, Monatshefte(11), 481-496. 29. Frost, R.L., Martens, W.N., and Kloprogge, J.T. (2002) Raman spectroscopic study of cinnabar (HgS), realgar (As4S4), and orpiment (As2S3) at 298 and 77K. Neues Jahrbuch fuer Mineralogie, Monatshefte(10),