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Diverse mineral assemblages of acidic alteration in the Rio Tinto area (southwest Spain): Implications for Mars

  • Christian Mavris , Javier Cuadros EMAIL logo , José Miguel Nieto , Janice L. Bishop and Joseph R. Michalski
Published/Copyright: November 28, 2018
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Abstract

Earth analogs are indispensable to investigate mineral assemblages on Mars because they enable detailed analysis of spectroscopic data from Mars and aid environmental interpretation. Samples from four sites in the Iberian Pyrite Belt (El Villar, Calañas, Quebrantahuesos, and Tharsis) were investigated using mineralogical, chemical, and spectroscopic techniques, with a focus on clay minerals and alteration environments. They represent Earth analogs of areas on Mars that underwent acidic alteration. X‑ray diffraction and transmittance mid-infrared data indicate that the rocks were subjected to several degrees of acid alteration corresponding to assemblages characterized by the following mixtures: (1) illite, chlorite, interstratified chlorite-vermiculite, kaolinite-smectite, and kaolinite; (2) illite, kaolinite, and alunite; and (3) jarosite and goethite. According to mineral stability data, these three assemblages correspond to pH values 7–5, 5–3, and <3, respectively. The lack of goethite in the illite-kaolinitealunite assemblage suggests an alteration in reducing conditions. Illite was progressively dissolved by acidic alteration but is sufficiently resilient not to be diagnostic of the intensity of the alteration. Illite and kaolinite were the two most abundant phyllosilicate minerals observed, and the main reaction involving phyllosilicates was the alteration of illite to kaolinite. Mixed-layer phases appeared mainly in the mildest degree of acid alteration, with few exceptions. This suggests a transition from a mechanism dominated by transformation to a mechanism dominated by dissolution-precipitation as the intensity of the acid alteration increases. Our results highlight the sparse kaolinite–alunite occurrences on Mars as worthy of specific investigation. Acid alteration on Mars is expected to be patchy and/or consisting of fine alteration rims. Alunite occurrences on Mars in the absence of goethite may indicate an acid alteration in reducing conditions. Kaolinite produced through acid alteration on Mars is expected to exist mainly as an end-member phase of low crystallinity, which would enhance IR absorption and increase its visibility.

Acknowledgments

This work was funded by the European Commission (Marie Curie Fellowship “Acid-Mars” to C.M.). We thank Raquel Vega for invaluable assistance in the field. The helpful comments of S. Potter-McIntyre and L. Baker are greatly appreciated.

References cited

Adamides, N.G. (2013) Rio Tinto (Iberian Pyrite Belt): a world-class mineral field reopens. Applied Earth Science: Transactions of the Institutions of Mining and Metallurgy B, 122, 2–15.10.1179/1743275813Y.0000000028Search in Google Scholar

Almodóvar, G.R., and Pérez-López, R. (2008) Recursos Minerales. In Geología de Huelva. Lugares de interés geológico. Servicio Publicaciones Universidad de Huelva, 184 pp.Search in Google Scholar

Altheide, T., Chevrier, V., and Noe Dobrea, E. (2010) Mineralogical characterization of acid weathered phyllosilicates with implications for secondary martian deposits. Geochimica et Cosmochimica Acta, 74, 6232–6248.10.1016/j.gca.2010.08.005Search in Google Scholar

Amils, R., Gonzalez-Toril, E., Fernandez-Remolar, D., Gomez, F., Aguilera, A., Rodriguez, N., Malki, M., Garcia-Moyano, A., Fairen, A.G., de la Fuente, V., and Sanz, J.L. (2007) Extreme environments as Mars terrestrial analogs: The Rio Tinto case. Planetary and Space Science, 55, 370–381.10.1016/j.pss.2006.02.006Search in Google Scholar

Arslan, C., and Arslan, F. (2003) Thermochemical review of jarosite and goethite stability regions at 25 and 95 °C. Turkish Journal of Engineering and Environmental Science, 27, 45–52.Search in Google Scholar

Aspandiar, M.F., and Eggleton, R.A. (2002a) Weathering of chlorite: I. Reactions and products in microsystems controlled by the primary mineral. Clays and Clay Minerals, 50, 685–698.10.1346/000986002762090227Search in Google Scholar

Aspandiar, M.F., and Eggleton, R.A. (2002b) Weathering of chlorite: II. Reactions and products in microsystems controlled by solution avenues. Clays and Clay Minerals, 50, 699–709.10.1346/000986002762090100Search in Google Scholar

Bibring, J.-P., Langevin, Y., Mustard, J.F., Poulet, F., Arvidson, R., Gendrin, A., Gondet, B., Mangold, N., Pinet, P., Forget, F., the OMEGA team, and others. (2006) Global mineralogical and aqueous Mars history derived from OMEGA/Mars Express data. Science, 312, 400–404. DOI: 10.1126/science.1122659.10.1126/science.1122659Search in Google Scholar

Bigham, J.M., Schwertmann, U., and Pfab, G. (1996) Influence of pH on mineral speciation in a bioreactor simulating acid mine drainage. Applied Geochemistry, 11, 845–849.10.1016/S0883-2927(96)00052-2Search in Google Scholar

Bishop, J.L., and Murad, E. (2005) The visible and infrared spectral properties of jarosite and alunite. American Mineralogist, 90, 1100–1107.10.2138/am.2005.1700Search in Google Scholar

Bishop, J.L., Noe Dobrea, E.Z., McKeown, N.K., Parente, M., Ehlmann, B.L., Michalski, J.R., Milliken, R.E., Poulet, F., Swayze, G.A., Mustard, J.F., and others. (2008) Phyllosilicate diversity and past aqueous activity revealed at Mawrth Vallis, Mars. Science, 321, 830–833.10.1126/science.1159699Search in Google Scholar PubMed PubMed Central

Bishop, J.L., Wray, J.J., Sessa, A.M., Danielsen, J.M., Ehlmann, B.L., Murchie, S.L., Horgan, B., Gross, C., Parente, M., and Seelos, F.P. (2018) Evidence of salty residues in layered outcrops at Mawrth Vallis and implications for evaporative environments on early Mars. Lunar and Planetary Science Confonference XLIX, The Woodlands, Texas, Abstract 1117.Search in Google Scholar

Brindley, G.W., Kao, C.-C., Harrison, J.L., Lipsicas, M., and Raythatha, R. (1986) Relation between structural disorder and other characteristics of kaolinites and dickites. Clays and Clay Minerals, 34, 239–249.10.1346/CCMN.1986.0340303Search in Google Scholar

Brown, J.B. (1971) Jarosite-geoethite stabilities at 25 °C, 1 ATM. Mineralium Deposita, 6, 245–252.10.1007/BF00208032Search in Google Scholar

Capitán, A., Nieto, J.M., Sáez, R., and Almodóvar, G.R. (2003) Caracterización textural y mineralógica del gossan de Filón Sur (Tharsis, Huelva). Boletín de la Sociedad Española de Mineralogía, 26, 45–58.Search in Google Scholar

Carter, J., Poulet, F., Bibring, J.-P., Mangold, N., and Murchie, S. (2013) Hydrous minerals on Mars as seen by the CRISM and OMEGA imaging spectrometers: Updated global view. Journal of Geophysical Research: Planets, 118, 831–858.10.1029/2012JE004145Search in Google Scholar

Cases, J.M., Bérend, I., François, M., Uriot, J.P., Michot, L.J., and Thomas, F. (1997) Mechanisms of adsorption and desorption of water vapor by homionic montmotillonite: 3. The Mg2+ Ca2+ Sr2+ and Ba2+ exchanged forms. Clays and Clay Minerals, 45, 8–22.10.1346/CCMN.1997.0450102Search in Google Scholar

Cuadros, J. (2012) Clay crystal-chemical adaptability and transformation mechanisms. Clay Minerals, 47, 147–164. DOI: 10.1180/claymin.2012.047.2.01.10.1180/claymin.2012.047.2.01Search in Google Scholar

Cuadros, J., Vega, R., and Toscano, A. (2015) Mid-infrared features of kaolinite-dickite. Clays and Clay Minerals, 63, 73–84.10.1346/CCMN.2015.0630201Search in Google Scholar

Das, G.K., Acharya, S., Anand, S., and Das., R.P. (1996) Jarosites: a review. Mineral Processing and Extractive Metallurgy Review, 16, 185–210.10.1080/08827509708914135Search in Google Scholar

de la Calle, C., and Suquet, H. (1988) Vermiculite. In S.W. Bailey, Eds., Hydrous Phyllosilicates, 19, p. 455–496. Reviews in Mineralogy, Mineralogical Society of America, Chantilly, Virginia.10.1515/9781501508998-017Search in Google Scholar

Ehlmann, B.L., and Mustard, J.F. (2012) An in-situ record of major environmental transitions on early Mars at Northeast Syrtis Major. Geophysical Research Letters, 39, L11202. DOI: 10.1029/2012GL051594.10.1029/2012GL051594Search in Google Scholar

Ehlmann, B.L., Mustard, J.F., Swayze, G.A., Clark, R.N., Bishop, J.L., Poulet, F., Des Marais, D.J., Roach, L.H., Milliken, R.E., Wray, J.J., and others. (2009) Identification of hydrated silicate minerals on Mars using MRO-CRISM: Geologic context near Nili Fossae and implications for aqueous alteration. Journal of Geophysical Research: Planets, 114, E00D08.10.1029/2009JE003339Search in Google Scholar

Ehlmann, B., Mustard, J.F., Murchie, S.L., Bibring, J.-P., Meunier, A., Fraeman, A.A., and Langevin, Y. (2011) Subsurface water and clay mineral formation during the early history of Mars. Nature, 479, 53–60.10.1038/nature10582Search in Google Scholar PubMed

Ehlmann, B.L., Swayze, G.A., Milliken, R.E., Mustard, J.F., Clark, R.N., Murchie, S.L., Breit, G.N., Wray, J.L., Gondet, B., Poulet, F., and others. (2016) Discovery of alunite in Cross crater, Terra Sirenum, Mars: Evidence for acidic, sulfurous waters. American Mineralogist, 101, 1527–1542.10.2138/am-2016-5574Search in Google Scholar

Elwood Madden, M.E., Bodnar, R.J., and Rimstidt, J.D. (2004) Jarosite as an indicator of water-limited chemical weathering on Mars. Nature, 431, 821–823.10.1038/nature02971Search in Google Scholar PubMed

Essalhi, M., Sizaret, S., Barbanson, L., Chen, Y., Lagroix, F., Demory, F., Nieto, J.M., Saez, R., and Capitan, M.A. (2011) A case study in the internal structure of the gossans and weathering processes in the Iberian Pyrite Belt using magnetic fabrics and paleomagnetic dating. Mineralium Deposita, 46, 981–999.10.1007/s00126-011-0361-8Search in Google Scholar

Farmer, V.C., Ed. (1974) The Infrared Spectra of Minerals, 539 p. Mineralogical Society Monograph 4, London.10.1180/mono-4Search in Google Scholar

Farmer, V.C., Ed. (1998) Differing effects of particle size and shape in the infrared and Raman spectra of kaolinite. Clay Minerals, 33, 601–604.10.1180/claymin.1998.033.4.07Search in Google Scholar

Farrand, W.H., Glotch, T.D., Rice, J.W. Jr., Hurowitz, J.A., and Swayze, G.A. (2009) Discovery of jarosite within the Mawrth Vallis region of Mars: Implications for the geologic history of the region. Icarus, 204, 478–488.10.1016/j.icarus.2009.07.014Search in Google Scholar

Fernandez-Remolar, D.C., Prieto-Ballesteros, O., Gomez-Ortiz, D., Fernandez-Sampedro, M., Sarrazin, P., Gailhanou, M., and Amils, R. (2011) Rio Tinto sedimentary mineral assemblages: A terrestrial perspective that suggests some formation pathways of phyllosilicates on Mars. Icarus, 211, 114–138.10.1016/j.icarus.2010.09.008Search in Google Scholar

Gainey, S.R., Hausrath, E.M., Hurowitz, J.A., and Milliken, R.E. (2014) Nontronie dissolution rates and implications for Mars. Geochimica et Cosmochimica Acta, 126, 192–211.10.1016/j.gca.2013.10.055Search in Google Scholar

Garrels, R.M., and Christ, C.L. (1965) Solutions, Minerals, and Equilibria, 450 p. Harper and Row, New York.Search in Google Scholar

Graf, H., Reichenbach, V., and Beyer, J. (1995) Dehydration and rehydration of vermiculites: II. Phlogopitic Ca-vermiculite. Clay Minerals, 30, 273–286.10.1180/claymin.1995.030.4.01Search in Google Scholar

Hemley, J.J., Hostetler, P.B., Gude, A.J., and Mountjoy, W.T. (1969) Some stability relations of alunite. Economic Geology and the Bulleting of the Society of Economic Geologists, 64, 599–612.10.2113/gsecongeo.64.6.599Search in Google Scholar

Huang, W.H., and Keller, W.D. (1973) New stability diagrams of some phyllosilicates in the SiO2-Al2O3-K2O-H2O system. Clays and Clay Minerals, 21, 331–336.10.1346/CCMN.1973.0210509Search in Google Scholar

Keith, W.J., Calk, L., and Ashley, R.P. (1979) Crystals of coexisting alunite and jarosite, Golfield, Nevada. Geological Survey Professional Paper 1124-C. U.S. Geological Survey.10.3133/pp1124CSearch in Google Scholar

Loizeau, D., Werner, S., Mangold, N., and Bibring, J.P. (2011) Ages of the clay-unit at Mawrth. 5th Mars Science Laboratory Landing Site Workshop.Search in Google Scholar

Martin-Izard, A., Arias, D., Arias, M., Gumiel, P., Sanderson, D.J., Castañon, C., Lavandeira, A., and Sanchez, J. (2015) A new 3D geological model and interpretation of structural evolution of the world-class Rio Tinto VMS deposit, Iberian Pyrite Belt (Spain). Ore Geology Reviews, 71, 457–476.10.1016/j.oregeorev.2015.06.006Search in Google Scholar

McKeown, N.K., Bishop, J.L., Noe dobrea, E.Z., Ehlmann, B.L., Parente, M., Mustard, J.F., Murchie, S.L., Swayze, G.A., and Bibring, J.-P. (2009) Characterization of phyllosilicates observed in the central Mawrth Vallis region, Mars, their potential formational processes, and implications for past climate. Journal of Geophysical Research: Planets, 114, DOI: 10.1029/2008JE003301.10.1029/2008JE003301Search in Google Scholar

McKeown, N.K., Bishop, J.L., Cuadros, J., Hillier, S., Amador, E., Makarewicz, H.D., Parente, M., and Silver, E.A. (2011) Interpretation of reflectance spectra of clay mineral-silica mixtures: implications for martian clay mineralogy at Mawrth Vallis. Clays and Clay Minerals, 59, 400–415. DOI: 10.1346/CCMN.2011.0590404.10.1346/CCMN.2011.0590404Search in Google Scholar

Michalski, J.R., Niles, P.B., Cuadros, J., and Balbridge, A.M. (2013) Multiple working hypotheses for the formation of compositional stratigraphy on Mars: Insights from the Mawrth Vallis region. Icarus, 226, 816–840. https://dx.doi.org/10.1016/j.icarus.2013.05.02410.1016/j.icarus.2013.05.024Search in Google Scholar

Moore, D.M., and Reynolds, R.C. Jr. (1997) X‑ray Diffraction and the Identification and Analysis of Clay Minerals, 2nd ed., 378 p. Oxford University Press, Oxford, U.K.Search in Google Scholar

Mosser-Ruck, R., Devineau, K., Charpentier, D., and Cathelineau, M. (2005) Effects of ethylene glycol saturation protocols on XRD patterns: a critical review and discussion. Clays and Clay Minerals, 6, 631–638.10.1346/CCMN.2005.0530609Search in Google Scholar

Murphy, P.J., Smith, A.M.L., Hudson-Edwards, K.A., Dubbin, W.E., and Wright, K. (2009) Raman and IR spectroscopic studies of alunite-supergroup compounds containing Al, Cr3+ Fe3+ and V3+ at the B site. Canadian Mineralogist, 47, 663–681.10.3749/canmin.47.3.663Search in Google Scholar

Noe Dobrea, E.Z., and Swayze, G. (2010) Acid pedogeneseis on Mars? Evidence for top-down alteration on Mars from CRISM and HiRISE data. 41st Lunar and Planetary Science Conference. Abstract 2620.Search in Google Scholar

Noe Dobrea, E.Z., Bishop, J.L., McKeown, N.K., Fu, R., Rossi, C.M., Michalski, J.R., Heinlein, C., Hanus, V., Poulet, F., Mustard, R.J.F., and others. (2010) Mineralogy and stratigraphy of phyllosilicate-bearing and dark mantling units in the greater Mawrth Vallis/west Arabia Terra area: Constraints on geological origin. Journal of Geophysical Research, 115, E00D19.10.1029/2009JE003351Search in Google Scholar

Roach, L.H., Mustard, J., Gendrine, A., Fernandez-Remolar, D., Amils, R., and Amaral-Zettler, L. (2006) Finding mineralogically interesting targets for exploration from spatially coarse visible and near IR spectra. Earth and Planetary Science Letters, 252, 201–214.10.1016/j.epsl.2006.09.044Search in Google Scholar

Russell, J.D., and Fraser, A.R. (1994) Infrared methods. In M.J. Wilson, Ed., Clay Mineralogy: Spectroscopic and chemical determinative methods, p. 13–67. Chapman & Hall, London.10.1007/978-94-011-0727-3_2Search in Google Scholar

Sáez, R., Almodóvar, G.R., and Pascual, E. (1996) Geological constraints on massive sulphide genesis in the Iberian Pyrite Belt. Ore Geology Reviews, 11, 429–451.10.1016/S0169-1368(96)00012-1Search in Google Scholar

Sejkora, J., Čejka, J., and Šrein, V. (2001) Pb dominant members of crandalite group from Cínovec and Moldava deposits, Krušné hory Mts. (Czech Republic). Journal of the Czech Geological Society, 46, 53–68.Search in Google Scholar

Sessa, A.M., Wray, J.J., and Bishop, J.L. (2018) Discovery of alunite in candidate ExoMars landing site, Mawrth Vallis: Evidence for localized evaporative environments. Lunar and Planetary Science Conference XLIX, The Woodlands, Texas, Abstract 2983.Search in Google Scholar

Sobron, P., Bishop, J.L., Blake, D.F., Chen, B., and Rull, F. (2014) Natural Fe-bearing oxides and sulfates from the Rio Tinto Mars analog site: Critical assessment of VNIR reflectance spectroscopy, laser Raman spectroscopy, and XRD as mineral identification tools. American Mineralogist, 99, 1199–1205.10.2138/am.2014.4595Search in Google Scholar

Thollot, P., Mangold, N., Ansan, V., Le Mouélic, S., Milliken, R.E., Bishop, J.L., Weitz, C.M., Roach, L.H., Mustard, J.F., and Murchie, S.L. (2012) Most Mars minerals in a nutshell: Various alteration phases formed in a single environment in Noctis Labyrinthus. Journal of Geophysical Research, 117, E00J06. DOI: 10.1029/2011je004028.10.1029/2011je004028Search in Google Scholar

Thompson, M., and Walsh, J.N. (2003) Handbook of Inductively Coupled Plasma Atomic Emission Spectrometry. Viridian, Woking, U.K.Search in Google Scholar

Toscano, M., Pascual, E., Nesbitt, R.W., and Donaire, T. (2014) Geochemical discrimination of hydrothermal and igneous zircon in the Iberian Pyrite Belt, Spain. Ore Geology Reviews, 56, 301–311.10.1016/j.oregeorev.2013.06.007Search in Google Scholar

Weitz, C.M., Bishop, J.L., Thollot, P., Mangold, N., and Roach, L.H. (2011) Diverse mineralogies in two troughs of Noctis Labyrinthus, Mars. Geology, 39, 899–902. doi: 10.1130/G32045.1.10.1130/G32045.1Search in Google Scholar

West, L., McGown, D.J., Onstott, T.C., Morris, R.V., Suchecki, P., and Pratt, L.M. (2009) High Lake gossan deposit: An Arctic analogue for ancient martian surficial processes? Planetary and Space Science, 57, 1302–1311.10.1016/j.pss.2009.05.011Search in Google Scholar

Wiseman, S.M., Arvidson, R.E., Murchie, S.L., Poulet, F., Andrews-Hanna, J.C., Morris, R.V., Seelos, F.P., and CRISM Team (2008) Phyllosilicate and hydrated sulfate deposits in Meridiani. 39th Lunar & Planetary Science Conference. Abstract 1806.Search in Google Scholar

Wray, J.J., Murchie, S.L., Squyres, S.W., Seelos, F.P., and Tornabene, L.L. (2009) Diverse aqueous environments on ancient Mars revealed in the southern highlands. Geology, 37, 1043–1046.10.1130/G30331A.1Search in Google Scholar

Received: 2017-10-13
Accepted: 2018-07-26
Published Online: 2018-11-28
Published in Print: 2018-12-19

© 2018 Walter de Gruyter GmbH, Berlin/Boston

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