A re-investigation on the historical cervantite-type antimony ochres

  1. Javier Garcia-Guinea
  2. Fernando Gervilla
  3. Fernando Garrido
  4. Virgilio Correcher
  5. Jose F. Marco
  6. Laura Tormo
Revista:
Estudios geológicos

ISSN: 0367-0449

Año de publicación: 2023

Volumen: 79

Número: 1

Tipo: Artículo

DOI: 10.3989/EGEOL.44775.621 DIALNET GOOGLE SCHOLAR lock_openAcceso abierto editor

Otras publicaciones en: Estudios geológicos

Resumen

Los ocres de antimonio son óxi-hidróxidos formados por meteorización de estibnita (Sb2S3). Normalmente aparecen como fases minerales simples cristalizadas en el sistema cúbico con estructura de tipo pirocloro y conteniendo algo de calcio y moléculas de agua en su red cristalina. Sus rangos composicionales pueden ser expresados por la fórmula: Sb5+ 2-x (Sb3+, Ca)y (O, OH, H2O)6-7, donde (y) está cerca de 1 y (x) va de 0 a 1. También es muy frecuente que los ocres de antimonio incluyan sustituciones de As, Fe, Ta, Ti, Cu y otros. Esta variabilidad química dentro de la misma estructura ha generado confusiones históricas de nombres de minerales equivalentes con patrones de difracción de rayos X muy similares siendo importante complementar con técnicas analíticas adicionales. El mineral-tipo cervantita de Cervantes (Lugo, España) (Ca, Sb3+)2(Sb5+)2O6(OH) fue desacreditado en 1954 y re-aprobado en 1962 como α-cervantita Sb3+Sb5+O4 difractando muestras de óxidos de antimonio sintéticos y naturales de otras localidades, como por ejemplo de Brasina (Serbia). En este trabajo estudiamos ambos minerales-tipo de Cervantes (Lugo, Spain) y de Zajaca-Stolice (Brasina, Serbia) desde los puntos de vista estructural, químico-elemental, termal, vibracional y de especiación química, asumiendo que los patrones de difracción de rayos X, los de la estructura tipo pirocloro son muy similares entre ellos. El espécimen tipo de Cervantes (Lugo) puede ser considerado como hydroxycalcioromeita (Ca,Sb3+)2(Sb5+)2O6(OH) mientras que el de Brasina Ca2(Sb5+)4O12(OH)2 es muy similar pero sin Sb3+. Ambas muestras contienen calcio y componentes hidratados, es decir, ambos están lejos de ser la α-Cervantita (Sb3+Sb5+O4) oficial anhidra y ortorrómbica. La espectroscopia micro-Raman es esencial para determinar fases minerales y vibraciones de enlaces Sb-O, mientras que espectroscopia FTIR y los ATD-TG fueron útiles para determinar grupos hidroxilos y aguas moleculares y la espectroscopia XPS para definir las especiaciones químicas del antimonio.

Información de financiación

Financiadores

Referencias bibliográficas

  • Abdel-Galil E.A.; El-Kenany W.M. & Hussin L.M.S. (2015). Preparation of nanostructured hydrated antimony oxide using a sol-gel process. Characterization and applications for sorption of La3+ and Sm3+ from aqueous solutions. Russian Journal of Applied Chemistry, 88(8): 1351-1360. https://doi.org/10.1134/S1070427215080200
  • Adelman, J.G.; Beauchemin, S.; Hendershot, W.H. & Kwong, Y.T.J. (2012). Change in the oxidation rate of stibnite as affected by pyrite in an oxygenated flow-through system. Geochemistry: Exploration, Environment, Analysis, 12: 227-239. https://doi.org/10.1144/1467-7873/11-RA-077
  • Ambe, S. (1987). Adsorption kinetics of antimony (V) ions onto α-Fe2O3 surfaces from an aqueous solution. Langmuir, 3(4): 489-493. https://doi.org/10.1021/la00076a009
  • Atencio D.; Andrade, M.B.; Christy, A.G.; Gieré, R. & Kartashow, P.M. (2010). The pyrochlore supergroup of minerals: nomenclature. Canadian Mineralogist, 48: 673-698. https://doi.org/10.3749/canmin.48.3.673
  • Báez, D.F.; Pardo H.; Laborda I.; Marco J.F.; Yáñez C. & Bollo S. (2017). Reduced graphene oxides: Influence of the reduction method on the electrocatalytic effect towards nucleic acid oxidation. Nanomaterials, 7 (7): 168. https://doi.org/10.3390/nano7070168 PMid:28677654 PMCid:PMC5535234
  • Bahfenne S. & Frost R.L. (2010). Raman spectroscopic study of the antimonate mineral lewisite (Ca, Fe, Na)2(Sb,Ti)2O6(O, OH)7. Radiation Effects and Defects in Solids, 165 (1): 46-53. https://doi.org/10.1080/10420150903418485
  • Bahfenne S. & Frost R.L. (2010). Vibrational Spectroscopic Study of the Antimonate Mineral Stibiconite. Spectroscopy Letters, 43 (6): 486-490. https://doi.org/10.1080/00387010903360313
  • Bahfenne S. & Frost R.L. (2010) Raman spectroscopic study of the antimonate mineral romeite. Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy, 75 (2): 637-639. https://doi.org/10.1016/j.saa.2009.11.031 PMid:20034848
  • Beudant F.S. (1837). Traité élémentaire de Minéralogie, 2nd edition, Carilian Jeune, Paris.
  • Biagioni C.; Orlandi P.; Nestola F. & Bianchin S. (2013). Oxycalcioroméite, Ca2Sb2O6O, from Buca della Vena mine, Apuan Alps, Tuscany, Italy: a new member of the pyrochlore supergroup. Mineralogical Magazine, 77 (7): 3027-3037. https://doi.org/10.1180/minmag.2013.077.7.12
  • Birchall T.; Connor J.A. & Hillier I (1975). High-energy photoelectron spectroscopy of some antimony compounds. Journal of the Chemical Society, Dalton Transactions, 20: 2003-2006. https://doi.org/10.1039/dt9750002003
  • Bodenes L.; A. Darwiche, L. Monconduit & Martinez H. (2015).The Solid Electrolyte Interphase a key parameter of the high performance of Sb in sodium-ion batteries: Comparative x-ray photoelectron spectroscopy study of Sb/Na-ion and Sb/Li-ion batteries. Journal of Power Sources, 273: 14-24. https://doi.org/10.1016/j.jpowsour.2014.09.037
  • Botto, L.; Schalamuk, I.; Ametrano, S. & De Barrio, R. (1990). The vibrational spectrum of Cervantite (α-Sb2O4). Anales de la Asociación Química Argentina, 78 (4): 195-201.
  • Burke, E.A.J. (2006) A mass discreditation of GQN minerals. Canadian Mineralogist, 44: 1557-1560. https://doi.org/10.2113/gscanmin.44.6.1557
  • Cody C.A.; L. Dicarlo & Darlington R.K. (1979). Vibrational and Thermal Study of Antimony Oxides. Inorganic Chemistry, 18 (6): 1572-1576. https://doi.org/10.1021/ic50196a036
  • Corby Anderson G. (2019). SME Mineral Processing and Extractive Metallurgy Handbook. Society for Mining, Metallurgy and Exploration, USA, 2203 pp.
  • Damour A. (1841). Sur la roméite, nouvelle espèce minérale, de St. Marcel, Piemont. Annales des Mines, 20 (3): 247-254. https://rruff.info/uploads/Annales_des_mines_20_1841_247.pdf
  • Dana J.D. (1850). A system of mineralogy: Comprising the most recent discoveries, 3rd edition. George P. Putnam, New York, London, 711 pp.
  • Delobel R.; H. Baussart & Leroy J.M. (1983). X-ray photoelectron spectroscopy study of uranium and antimony mixed metal-oxide catalysts. Journal of the Chemical Society, Faraday Transactions, 79: 879-891. https://doi.org/10.1039/f19837900879
  • Gadsden J.A. (1975). Infrared spectra of minerals and related inorganic compounds. Buttherworth & CO, London, 277 pp.
  • Garbassi F. (1980). XPS and AES Study of Antimony Oxides. Surface and interface analysis, 5(2): 165-169. https://doi.org/10.1002/sia.740020502
  • Garcia-Guinea J.; Garrido F.; López-Arce P.; Correcher V. & Delafiguera J. (2017). Spectral green cathodoluminescence emission from surfaces of insulators with metal-hydroxyl bonds. Journal of Luminescence, 190: 128-135. https://doi.org/10.1016/j.jlumin.2017.05.039
  • Garcia-Guinea J.; Correcher V.; Can N.; Garrido F. & Townsend P.D. (2018). Cathodoluminescence spectra recorded from surfaces of solids with hydrous molecules. Journal of Electron Spectroscopy and Related Phenomena, 227: 1-8. https://doi.org/10.1016/j.elspec.2018.05.008
  • Gilliam S.J.; Jensen J.O.; Banerjee A.; Zeroka D.; Kirkby S.J. & Merrow C.N. (2004). A theoretical and experimental study of Sb4O6: vibrational analysis, infrared and Raman spectra. Spectrochimica Acta Part A: Molecular Spectroscopy, 60: 425-434 https://doi.org/10.1016/S1386-1425(03)00245-2 PMid:14670509
  • Gottlieb P.; Wilkie G.; Sutherland D.; Ho-Tun E.; Suthers S.; Perera K.; Jenkins B.; Spencer S.; Butcher A. & Rayner J. (2000). Using quantitative electron microscopy for process mineralogy applications. The Journal of the Minerals, Metals and Materials Society, 52: 24-25 https://doi.org/10.1007/s11837-000-0126-9
  • Gründer W.; Pätzold H. & Strunz H. (1962). Sb2O4 als Mineral (Cervantit). Neues Jahrbuch für Mineralogie / Monatshefte, 5: 93-98.
  • Gunasekaran S, G. Anbalagan, G. & Pandi S. (2006). Raman and infrared spectra of carbonates of calcite structure. Journal of the Raman Spectroscopy, 37: 892-899 https://doi.org/10.1002/jrs.1518
  • Hussak E. & Prior G.T. (2018) Lewisite and zirkelite, two new Brazilian minerals. Mineralogical Magazine, 11: 80-88. https://doi.org/10.1180/minmag.1895.011.50.05
  • Izquierdo R.; Sacher E. & Yelon A. (1989). X-ray photoelectron spectra of antimony oxides. Applied Surface Science, 40: 175-177. https://doi.org/10.1016/0169-4332(89)90173-6
  • Kharbish S. & Jelen S. (2016). Raman spectroscopy of the Pb-Sb sulfosalts minerals: Boulangerite, jamesonite, robinsonite and zinkenite. Vibrational Spectroscopy, 85: 157-166. https://doi.org/10.1016/j.vibspec.2016.04.016
  • Li N.; Xia Y.; Mao Z.; Wang L.; Guan Y. & Zheng A. (2012) Influence of antimony oxide on flammability of polypropylene/intumescent flame retardant system. Polymer Degradation and Stability, 97(9): 1737-1744. https://doi.org/10.1016/j.polymdegradstab.2012.06.011
  • López G.P.; Castuer D.G. & Ratner B. (1991). XPS O1s binding energies for polymers containing hydroxyl, ether, ketone and ester groups. Surface and Interface Analysis, 17: 267-272. https://doi.org/10.1002/sia.740170508
  • Makreski P.; G. Petrusevski, S. Ugarkovic & G. Jovanovski (2013) Laser-induced transformation of stibnite (Sb2S3) and other structurally related salts. Vibrational Spectroscopy 68: 177-182. https://doi.org/10.1016/j.vibspec.2013.07.007
  • Marco J.F.; Gancedo J.R.; Ortiz J. & Gautier J.L. (2004). Characterization of the spinel-related oxides NixCO3−xO4 (x=0.3,1.3,1.8) prepared by spray pyrolysis at 350°C. Applied Surface Science, 227: 175-186. https://doi.org/10.1016/j.apsusc.2003.11.065
  • Meškinis S.; Vasiliauskas A.; Andrulevičius M.; Peckus D.; Tamulevičius S. & Viskontas K. (2020). Diamond like carbon films containing Si: Structure and nonlinear optical properties. Materials, 13 (4): 1-15. https://doi.org/10.3390/ma13041003 PMid:32102249 PMCid:PMC7079637
  • Martín, J.D. (2006). XPowder: Programa para análisis cualitativo y cuantitativo por difracción de rayos X. Macla, 4: 35-44.
  • Miller, P.J. & Cody C.A. (1982). Infrared and Raman investigation of vitreous antimony trioxide. Spectrochimica Acta Part A: Molecular Spectroscopy, 38(5): 555-559 https://doi.org/10.1016/0584-8539(82)80146-3
  • Morgan W.E.; Stec, W.J. & Van Wazer J.R. (1973). Inner-orbital binding-energy shifts of antimony and bismuth compounds. Inorganic Chemistry, 12(4): 953-955. https://doi.org/10.1021/ic50122a054
  • Moulder J.F.; Stickle W.F.; Sobol P.E. & Bomben K.D. (1992) Handbook of X-ray Photoelectron Spectroscopy. Perkin-Elmer, Eden Prairie, USA, 261 pp.
  • Vitaliano C.J. & Mason B. (1952). Stibiconite and Cervantite. American Mineralogist, 37: 982-999. http://www.minsocam.org/ammin/AM37/AM37_982.pdf
  • Multani R.S.; Feldmann T. & Demopoulos G.P. (2016). Antimony in the metallurgical industry: A review of its chemistry and environmental stabilization options. Hydrometallurgy 164: 141-153. https://doi.org/10.1016/j.hydromet.2016.06.014
  • Orecchio S. (2013) Micro-analytical characterization of decorations in handmade ancient floor tiles using inductively coupled plasma optical emission spectrometry (ICP-OES). Microchemical Journal, 108: 137-150. https://doi.org/10.1016/j.microc.2012.10.011
  • Rouse R.C.; Dunn P.J.; Peacor Dr. & Wang L. (1998), Structural studies of the natural antimonian pyrochlores. I. Mixed valency, cation site splitting, and symmetry reduction in lewisite. Journal of Solid State Chemistry, 141: 562-569. https://doi.org/10.1006/jssc.1998.8019
  • Schaller W.T. (1916). Mineralogical notes. Schneebergite and Romeite. U.S. Geological Survey Bulletin, 610: 81-95 https://pubs.usgs.gov/bul/0610/report.pdf
  • Fleischer M (1962). New mineral names. American Mineralogist, 47(9-10): 1216-1223.
  • Siebert H. (1959). Infrared spectra of telluric acids, tellurates and antimonates. Zeitschrift für anorganische und Allgemeine Chemie, 301: 161-170. https://doi.org/10.1002/zaac.19593010305
  • Smirnov M.Y.; A.V. Kalinkin & V.I. Bukhtiyarov (2007). X-ray photoelectron spectroscopic study of the interaction of supported metal catalysts with NOx. Journal of Structural Chemistry, 48: 1053-1060 https://doi.org/10.1007/s10947-007-0170-1
  • Stevens J.G.; Etter R.M. & Setzer E.W. (1993). 121Sb Mössbauer spectroscopic study of the mineral stibiconite. Nuclear Instruments and Methods in Physics Research B, 76: 252-253. https://doi.org/10.1016/0168-583X(93)95199-F
  • Stevens-Kalceff M.A. & Phillips M.R. (1995). Cathodoluminescence micro-characterization of the defect structure of quartz. Physical Review B., 52: 3122-3134 https://doi.org/10.1103/PhysRevB.52.3122 PMid:9981428
  • Wagner C.D.; Naumkin A.V.; Kraut-Vass A.; Allison J.W.; Powell C.J. & Rumble J.R. Jr. (2003) NIST Standard Reference Database 20, Version 3.4, web version. http:/srdata.nist.gov/xps/
  • Wilson S.C.; P.V. Lockwood, P.M. Ashley &Tighe M. (2010). The chemistry and behavior of antimony in the soil environment with comparisons to arsenic: A critical review. Environmental Pollution, 158 (5): 1169-1181, https://doi.org/10.1016/j.envpol.2009.10.045 PMid:19914753
  • Zubkova V.; D.Y. Pushcharowsky, D. Atencio, A.V. Arakcheeva & P.A. Matioli. (2000) The crystal structure of lewisite, (Ca,Sb3+,Fe3+,Al,Na,Mn)2(Sb5+,Ti)2O6(OH). Journal of Alloys and Compounds, 296: 75-79. https://doi.org/10.1016/S0925-8388(99)00513-7