Mineralogical Applications
of Synchrotron Radiation
Much of our work utilizes synchrotron X-radiation in the study of trace elements in minerals. Most of this has been done at the National Synchrotron Light Source I & II (NSLS & NSLSII), Brookhaven National Laboratory, and the Advanced Photon Source (APS), Argonne, National Laboratory.
Advanced Photon Source National Synchrotron Light Source II
Tender-Energy Microspectroscopy Consortium NSLSII (beamline 8-BM)
Sulfur K-edge XANES from natural fluorapatite collected at the TES beamline 8-BM of the NSLSII.
Analytical techniques include:
Spatially resolved synchrotron X-ray fluorescence microanalysis (SXRFMA) for determination of trace element distributions in sectorally and intrasectorally zoned minerals;
Intrasectoral zoning of La in apatite from the Golconda Mine, Minas Gerias Brazil. A) Three sided Growth hillock on the (100) crystal face. B) CL showing distinct zoning between vicinal faces and associated subsectors of the hillock in A. C) SXRFMA data showing the concentration difference of La between the symmetrically nonequivalent subsectors. Intrasectoral zoning of La and Sm in apatite from Llallagua, Bolivia. Left) SXRFMA data showing the concentration difference in La and Sm between the symmetrically nonequivalent subsectors of the hillock shown on the right. Right) Three sided Growth hillock on the (100) crystal face. SXRFMA data were taken in a line scan from a to b between the 011 and 001 vicinal faces and their associated subsectors.
Sectoral zoning of Sr in fluorite from the Mex Tex Mine, Bingham, NM. Left) Optical photomicrograph of a thin section through a single crystal of fluorite. Different sectors are apparent from color differences. Right) SXRFMA area scan showing the differential concentration of Sr between the symmetrically nonequivalent sectors. Higher concentration is indicated by brighter color. Sectoral zoning of Sr in fluorite from the Royal Flush, Bingham, NM. Left) Optical photomicrograph of a thin section through a single crystal of fluorite. Different sectors are apparent from color differences. Right) SXRFMA area scan showing the differential concentration of Sr between the symmetrically nonequivalent sectors. Higher concentration is indicated by brighter color.
X-ray absorption spectroscopy (XANES and EXAFS) for evaluation of trace metal oxidation state and site occupancy.
Curve-fit Eu L3-edge XANES data for the Llallagua apatite showing the presence of both divalent and trivalent Eu.
U L3-edge XANES data for synthetic U(VI):apatite, UO2 and uranyl nitrate, showing an unusual edge structure of U(VI) in apatite. EXAFS Fourier transform magnitudes (not corrected for phase shifts) of U(VI) in synthetic fluorapatite. The large peak corresponds to a U-O distance of 2.06 Å.
(Left) Geometry of the Ca1 site in fluorapatite viewed down [001] with bond distances indicated. (Right) Experimentally (EXAFS) determined U-O distance and speculated distortion of the Ca1 site occupied by U(VI). 8-BM NSLSII GSECARS Sector 13 at the APS Synchrotron Sources on the WWW Synchrotron Publications: For reprints email John Rakovan at Rakovajf@muohio.edu
Luo*, Y., Rakovan, J., Elzinga, E., Pan, Y., Lupulescu, M.V., and Hughes, J. (2011). Crystal chemistry of Th in fluorapatite. American Mineralogist. 96:23-33.
Borkiewicz*, O., Rakovan, J., and Cahill, C. (2010) Time resolved in-situ studies of apatite formation pathways in aqueous solutions. American Mineralogist, 95:1224-1236.
Luo*, Y., Rakovan, J., Hughes, J. Pan, Y., (2009). Site preference of U and Th in Cl, F, Sr apatites . American Mineralogist, 94: 345-351.
Rakovan, J. Luo, Y and Borkiewicz, O. (2008) Synchrotron Microanalytical Methods in the Study of Trace and Minor Elements in Apatite. Mineralogia, 39:31-40.
Meng, Y., Newville, M., Sutton, S., Rakovan, J, and Mao, H.K. (2003) Fe and Ni impurities in synthetic diamond. American Mineralogist. 88, 1555-1559.
Rakovan, J., Reeder, R.J., Elzinga, E.J., Cherniak, D. Tait, C.D. and Morris, D.E. (2002) Characterization of U(VI) in the apatite structure by X-ray absorption spectroscopy. Environmental Science and Technology. 36, 3114-3117.
Bosze, S. and Rakovan, J. (2002) Surface structure controlled sectoral zoning of the Rare Earth Elements in fluorite from Long Lake, N.Y. and Bingham, N.M. Geochim. Cosmochim. Acta. 66, 997-1009.
Rakovan, J., M. Newville and S. Sutton (2001) Evidence of heterovalent europium in zoned Llallagua apatite using wavelength dispersive XANES. American Mineralogist, 86, 697-700.
Reeder, R.J. and Rakovan, J. (1999) Surface structural controls on trace element incorporation
during crystal growth. In Growth, Dissolution and Pattern-formation in Geosystems, B. Jamtveitand P. Meakin (eds.) p. 143-162. Kluwer Academic Publishers.Rakovan, J., McDaniel, D.K., and Reeder R.J. (1997) Use of surface-controlled REE sectoral
zoning in apatite from Llallagua, Bolivia, to determine a single-crystal Sm-Nd age. Earth and Planetary Science Letters,146, 329-336.Rakovan, J., and Reeder, R.J. (1996) Intracrystalline Rare Earth Element distributions in apatite:
Surface structural influences on zoning during Growth. Geochim. Cosmochim. Acta, 60, 4435-4445.Rakovan, J., and Reeder, R.J. (1994) Differential incorporation of trace elements and
dissymmetrization in apatite: The role of surface structure during growth. American Mineralogist, 79, 892-903.Parise, J.B., Corbin, D.R., Abrams, L., Northrup, P., Rakovan, J., Nenoff, T.M., and Stucky, G.D.
(1994) Structural relationships between some BePO-, BeAsO-, and AlSiO-RHO frameworks. Zeolites, 14, 25- 34.Borkiewicz*, O., Rakovan, J. and Cahill, C. L. (2006) Kinetics and pathways of apatite formation - In-situ time resolved studies. Annual Geological Society of America meeting, Abstracts with program.
Rakovan, J., Luo*, Y., Elzinga, E.J., Pan, Y., Lupulescu, M., and Hughes, J.M. (2006) Site distribution and structural state of Th in fluoroapatite determined by single crystal XRD and EXAFS. International Mineralogical Association meeting in Kobe Japan, Abstracts with Program.
Luo*, Y., Rakovan, J., Elzinga, E.J., Pan, Y., and Hughes, J.M. (2006) Crystal chemistry of Th in apatite: Geochemistry and environmental implications. American Geophysical Union annual Spring meeting, Abstracts with Program.
Borkiewicz*, O., Rakovan, J. and Cahill, C. L. (2006) In-situ time resolved studies of apatite formation pathways - implications for biological and environmental systems. American Geophysical Union annual Spring meeting, Abstracts with Program.
Rakovan, J., Luo, Y., Elzinga, E.J., Pan, Y., Lupulescu, M., and Hughes, J.M. (2005) Structural state of Th in
fluoroapatite determined by single crystal XRD and EXAFS. Goldschmidt Conference Abstracts with Program.Rakovan, J. (2003) Lanthanides in Fluorite (REE:CaF2): Probes of Crystal Surface Structure and Association in Color Centers. Materials Research Society National Meeting Program and Abstracts.
Rakovan, J., Reeder, R.J., Elzinga, E.J., Cherniak, D. Tait, C.D. and Morris, D.E. (2002) Crystal Chemistry of U(VI) in Apatite Determined by X-ray Absorption Spectroscopy. Annual Geological Society of America meeting, Abstracts with program.
Rakovan, J., Bosze, S., and Lanzirotti, A. (2001) Evaluating Heterogeneous Reactivity at the Mineral-Water Interface from Sectoral Zoning of REEs, Sr and Y in Fluorite. Research Highlights, National Synchrotron Light Source 2000 Activity Report, 2-53 - 2-56.
Rakovan, J., Sutton, S. Newville, M. and Lanzirotti, A. (2001) The use of WDS in Synchrotron X-ray
Fluorescence and Spectroscopy: Case studies involving heterogeneous reactivity at the Mineral-Water Interface. 2001 Goldschmidt Conference Abstracts with Program.Rakovan, J., Newville, M. and Sutton, S. (2000) Evaluation of Europium Oxidation State and Anomalous Partitioning Behavior in Intrasectorally Zoned Apatite Using Wavelength Dispersive Micro-XANES. Advanced Photon Source Activity Report 2000. Link
Bosze, S. and Rakovan, J. (1999) Surface Controlled Heterogeneous Incorporation of REE, Sr
and Y in Fluorite. Annual Geological Society of America meeting, Abstracts with program. p.A-358.Bosze, S., Rakovan, J., Shea, G, and Lanzirotti, A.(1999) Wavelength dispersive SXRFMA of
sectorally distributed REE heterogeneities in fluorite. National Synchrotron Light Source 1999
Activity Report.Rakovan, J. (1998) Sectoral zoning (SZ) of REEs in fluorite: Indication of the heterogeneous
nature and distribution of surface protosites. International Mineralogical Association Program with
Abstracts. A83.Rakovan, J. and Shea, G. (1998) SXRFMA of Sectoral Zoning of Trace Elements in
Hydrothermal Fluorite Crystals. National Synchrotron Light Source 1998 Activity Report.Rakovan, J. and Reeder, R. J. (1996) Spatially Resolved Trace Element Heterogeneities in
Apatite Measured via Synchrotron X-ray Fluorescence Microanalysis. National Synchrotron Light
Source 1996 Activity Report. B-299Rakovan, J. and Reeder, R. J. (1994) Differential incorporation of trace elements during growth
of grossular and apatite: intrasectoral zoning vs. dissymmetrization. National Synchrotron Light
Source 1994 Activity Report. B-185.Rakovan, J., and Leinenweber, K. (1993) Dehydroxylation of Mg-rich chlorite at 2.5 and 4.1
Gpa. National Synchrotron Light Source Annual Report, p.B-131.Rakovan, J., Northrup, P., and Reeder, R. J. (1993) Surface structural controls on trace element
incorporation during growth of minerals. National Synchrotron Light Source Activity Report, p.B-225.Lanzirotti, A., Hanson G.N., Northrup, P., Reeder, R.J. and Rakovan, J. (1993) Monazite
breakdown in chlorite schists National Synchrotron Light Source Activity Report.Parise, J.B., Leinenweber, K. Weidner, D.J., Rakovan, J. Vaughan, M., Gwanmesia, G., and
Liebermann, R.C. (1991) Preliminary studies of the potential for structure refinement at high
pressures using the DIA apparatus: SiO2, stishovite, at high pressure. National Synchrotron Light
Source Annual Report, p221.
