Abstract
Limonite is mainly derived from weathering of Fe sulfide, iron-bearing carbonate, or silicate minerals. The weathering of Fe sulfide or carbonate minerals to yield limonite from the Tongling mineralization cluster has been studied extensively. Knowledge of the mineralogical and geochemical characteristics of the limonite from weathering of Fe-bearing silicate minerals is still incomplete, however. To address this, black limonite containing ilvaite (a silicate mineral) found in Yeshan iron deposit, Tongling, China, was studied using mineralogical and chemical analysis. The mineralogical characteristics indicated that Mn goethite was present as nano-granular (<15 nm) or acicular (50–100 nm long, ~10 nm wide, i.e. high length/width ratio) crystals with low crystallinity. Groutite, ramsdellite, and pyrolusite were identified in the limonite as ~5 nm nanoparticles, and coated on the goethite surface. Amorphous Fe-Mn phases and silica were highly developed in the limonite studied. Ilvaite crystals showed idiomorphic granular morphology and were replaced by Fe-Mn oxides/hydroxides; pyrite was also present as inclusions within the ilvaite and the ilvaite structural formula calculated was Ca1.04(Fe1.57Mn0.31Mg0.04)(Fe1.09Al0.01)[Si1.95O]O(OH). According to the relatively high CuO and ZnO values and the low Al2O3 value in the black limonite, the negative correlations between (Fe2O3+MnO) and (CuO+ZnO+BaO), (Fe2O3+MnO) and Al2O3, high Mn and Si contents, and the characteristics of the textural relationships and compositions between the black limonite and ilvaite, a semi-enclosed environment with acidic to weakly alkaline conditions was deduced; ilvaite was found to be responsible for the formation and enrichment of limonite.
Similar content being viewed by others
References
Abe, H. (1972) Chemical compositions of altered rocks surrounding volcanogenic limonite deposits of the Abuta mine, Hokkaido. The Journal of the Japanese Association of Mineralogists, Petrologists and Economic Geologists, 67, 352–356.
Agata, T. and Adachi, M. (1995) Ilvaite from a serpentinized peridotite in the Asama igneous complex, Mikabu greenstone belt, Sambagawa metamorphic terrain, central Japan. Mineralogical Magazine, 59, 489–496.
Alvarez, M., Sileo, E.E., and Rueda, E. H. (2005) Effect of Mn (II) incorporation on the transformation of ferrihydrite to goethite. Chemical Geology, 216, 89–97.
Alvarez, M., Tufo, A.E., Zenobi, C., Ramos, C.P., and Sileo, E.E., (2015) Chemical, structural and hyperfine characterization of goethites with simultaneous incorporation of manganese, cobalt and aluminum ions. Chemical Geology, 414, 16–27.
Andreu, E., Torró, L., Proenza, J.A., Domenech, C., García-Casco, A., Benavent, C.V.D., Chavez, C., Espaillat, J., and Lewis, J.F. (2015) Weathering profile of the Cerro de Maimón VMS deposit (Dominican Republic): textures, mineralogy, gossan evolution and mobility of gold and silver. Ore Geology Reviews, 65, 165–179.
Baioumy, H.M., Khedr, M.Z., and Ahmed, A.H. (2013) Mineralogy, geochemistry and origin of Mn in the high- Mn iron ores, Bahariya Oasis, Egypt. Ore Geology Reviews, 53, 63–76.
Barrett, T.J. and Friedrichsen, H. (1982) Elemental and isotopic compositions of some metalliferous and pelagic sediment from the Galapagos Mounds area, DSDP Leg 70. Chemical Geology, 36, 275–298.
Blanchard, R. and Boswell, P.F. (1935) “Limonite” of molybdenite derivation. Economic Geology, 30, 313–319.
Bonev, I.K., Vassileva, R.D., Zotov, N., and Kouzmanov, K. (2005) Manganilvaite, CaFe2+Fe3+(Mn, Fe2+)(Si2O7)O(OH), a new mineral in the ilvaite group, from Pb-Zn skarn deposits in the Rhodope Mountains, Bulgaria. The Canadian Mineralogist, 43, 1027–1042.
Bowell, R.J. (2010) Sulfide oxidation and production of gossans, Ashanti mine, Ghana. International Geology Review, 36, 732–752.
Burgos, W.D., Borch, T., Troyer, L.D., Luan, F., Larson, L.N., Brown, J.F., Lambson, J., and Shimizu, M. (2012) Schwertmannite and Fe oxides formed by biological lowpH Fe (II) oxidation versus abiotic neutralization: impact on trace metal sequestration. Geochimica et Cosmochimica Acta, 76, 29–44.
Bustamante, A., Cabrera, J., Garcia, V., Urday, E., Abdu, Y.A., and Scorzelli, R.B. (2005) Mössbauer spectroscopy description of limonite from Taraco, in the Huancane province of the Puno region, Peru. Hyperfine Interactions, 166, 593–597.
Cai, J.H. (2006) Gold occurrence in a gossan type gold deposit in Tongling, Anhui. Mineral Resources and Geology, 20, 283–286 (in Chinese).
Cao, X.S. and Kong, D.F. (1991) Zoning characterics and metallogeny of the gossan gold deposit at Xinqiao, Tongling, Anhui. Contributions to Geology and Mineral Resources Research, 6, 71–79 (in Chinese).
Carlo, E.H.D., McMurtry, G.M., and Yeh, H.W. (1983) Geochemistry of hydrothermal deposits from Loihi submarine volcano, Hawaii. Earth and Planetary Science Letters, 66, 438–449.
Chen, P., Chen, T.H., Xu, L., Liu, H.B., and Xie, Q.Q. (2017) Mn-rich limonite from the Yeshan Iron Deposit, Tongling District, China: A natural nanocomposite. Journal of Nanoscience and Nanotechnology, 17, 6931–6935.
Colin, F., Nahon, D., Trescases, J.J., and Melfi, A.J. (1990) Lateritic weathering of pyroxenites at Niquelandia, Goias, Brazil: the supergene behavior of nickel. Economic Geology, 85, 1010–1023.
Conrad, C.F., Icopini, G.A., Yasuhara, H., Bandstra, J.Z., Brantley, S.L., and Heaney, P.J. (2007) Modeling the kinetics of silica nanocolloid formation and precipitation in geologically relevant aqueous solutions. Geochimica et Cosmochimica Acta, 71, 531–542.
Cornell, R.M. (1987) Effect of silicate species on the transformation of ferrihydrite into goethite and hematite in alkaline media. Clays and Clay Minerals, 35, 21–28.
Cornell, R.M. and Schwertmann, U. (2003) The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses. Wiley-VCH, Germany, pp. 433–475.
Dubiková, M., Cambier, P., Šucha, V., and ČaploviČová, M. (2002) Experimental soil acidification. Applied Geochemistry, 17, 245–257.
Dymond, J., Corliss, J.B., Cobler, R., Muratli, C.M., Chou, C., and Conard, R. (1980) Composition and origin of sediments recovered by deep drilling of sediment mounds, Galapagos Spreading Center. In Initial Reports of Deep Sea Drilling Project, Vol. 54, (B.R. Rosenthal et al., editors). U.S. Government Printing Office, Washington D.C., pp. 377–38
Ebinger, M.H. (1989) Mn-substituted goethite and Fe-substituted groutite synthesized at acid pH. Clays and Clay Minerals, 37, 151–156.
Embrechts, J. and Stoops, G. (1982) Microscopical aspects of garnet weathering in a humidtropical environment. European Journal of Soil Science, 33, 535–545.
Endo, S. (2017) Ilvaite-manganilvaite series minerals in jasper and iron-manganese ore from the Northern Chichibu belt, central Shikoku, Japan. Journal of Mineralogical and Petrological Sciences, 112, 166–174.
España, J.S., Pamo, E.L., Santofimia, E., Aduvire, O., Reyes, J., and Barettino, D. (2005) Acid mine drainage in the Iberian Pyrite Belt (Odiel river watershed, Huelva, SW Spain): geochemistry, mineralogy and environmental implications. Applied Geochemistry, 20, 1320–1356.
Essalhi, M., Sizaret, S., Barbanson, L., Chen, Y., Lagroix, F., Demory, F., Nieto, J.L., Saez, R., and Capitan, M.A. (2011) A case study of the internal structures of gossans and weathering processes in the Iberian Pyrite Belt using magnetic fabrics and paleomagnetic dating. Mineralium Deposita, 46, 981–999.
Franchini, M.B. (2002) First occurrence of ilvaite in a gold skarn deposit. Economic Geology and the Bulletin of the Society of Economic Geologists, 97, 1119–1126.
Frost, R.L., Ding, Z., and Ruan, H.D. (2003) Thermal analysis of goethite. Journal of Thermal Analysis and Calorimetry, 71, 783–797.
Frisbee, N.M. and Hossner, L.R. (1995) Siderite weathering in acidic solutions under carbon dioxide, air, and oxygen. Journal of Environmental Quality, 24, 856–860.
Geologic map of Tongling, Anhui Province in 1:50000 (1989) No. 321 of Bureau of Geology and Mineral Exploration of Anhui Province (in Chinese).
Gualtieri, A.F. and Venturelli, P. (1999) In situ study of the goethite-hematite phase transformation by real time synchrotron powder diffraction. American Mineralogist, 84, 895–904.
Güner, S., Amir, M., Geleri, M., Sertkol, M., and Baykal, A. (2015) Magneto-optical properties of Mn3+ substituted Fe3O4 nanoparticles. Ceramics International, 41, 10915–10922.
Harder, H. (1976) Nontronite synthesis at low temperatures. Chemical Geology, 18, 169–180.
Harder, H. (1977) Clay mineral formation under lateritic conditions. Clay Minerals, 12, 281–299.
Harder, H. (1978) Synthesis of iron layer silicate minerals under natural conditions. Clays and Clay Minerals, 26, 65–72.
He, J.R., Yao, Z.Y., Li, Y., Sun, N.G., and Dai, A.H. (1992) A comprehensive exploration of gossan type gold deposit in the Middle-Lower Yangtze area. Geology and Prospecting, 28, 27–33 (in Chinese).
Kaneko, T., Sugita, S., Tamura, M., Shimasaki, K., Makino, E., and Silalahi, L.H. (2002) Highly active limonite catalysts for direct coal liquefaction. Fuel, 81, 1541–1549.
Kelly, W.C. (1957) Mineralogy of limonite in lead-zinc gossans. Economic Geology, 52, 536–545.
Kiczka, M., Wiederhold, J.G., Frommer, J., Voegelin, A., Kraemer, S.M., Bourdon, B., and Kretzschmar, R. (2011) Iron speciation and isotope fractionation during silicate weathering and soil formation in an Alpine glacier forefield chronosequence. Geochimica et Cosmochimica Acta, 75, 5559–5573.
Koch, C.B., Morup, S., Madsen, M.B., and Vistisen, L. (1995) Iron-containing weathering products of basalt in a cold, dry climate. Chemical Geology, 122, 109–119.
Li, J.W., Vasconcelos, P., Duzgoren-Aydin, N., Yan, D.R., Zhang, W., Deng, X.D., Zhao, X.F., Zeng, Z.P., and Hu, M.A. (2007) Neogene weathering and supergene manganese enrichment in subtropical South China: an 40Ar/39Ar approach and paleoclimatic significance. Earth and Planetary Science Letters, 256, 389–402.
Li, L., Morishita, K., and Takarada, T. (2007) Light fuel gas production from nascent coal volatiles using a natural limonite ore. Fuel, 86, 1570–1576.
Li, W.D. (1980) Studies on the Development of Oxidation of the Sulfide Ore Deposits in the Middle Lower Yangze Area. Geological Publishing House, Beijing, China, pp. 36–117 (in Chinese)
Li, Y., He, J.R., Sun, N.G., and Yao, Z.Y. (1992) Gossan-Type Gold Deposit of Middle-Lower Yangtze Area. Geological Publishing House, Beijing, China, pp. 6–42 pp. (in Chinese).
Liu, H.B., Chen, T.H., Zou, X.H., Qing, C.S., and Frost, R.L. (2013) Thermal treatment of natural goethite: thermal transformation and physical properties. Thermochimica Acta, 568, 115–121.
Liu, H.B., Chen, T.H., and Frost, R.L. (2014) An overview of the role of goethite surfaces in the environment. Chemosphere, 103, 1–11.
Liu, S.B. (2016) Nanomineralogy and Geochemistry of Limonite of Xinqiao Ore-field in Tongling, Anhui Province. Masters dissertation, Hefei University of Technology, China, pp. 21–54.
Liu, T.M. (1989) Study on the properties and occurrence state of Au in the gossan gold ore from mountain Huang Shialao, Tongling City, Anhui Province. Metallurgical Geology of Central South, 2, 28–33 (in Chinese).
Liu, Y.S. (2010) Continental and oceanic crust recyclinginduced melt-peridotite interactions in the trans-north China orogen: U-Pb dating, Hf isotopes and trace elements in zircons from mantle xenoliths. Journal of Petrology, 51, 392–399.
Liu, Y.S., Hu, Z.C., Gao, S., Günther, D., Xu, J., Gao, C.G., and Chen, H.H. (2008) In situ, analysis of major and trace elements of anhydrous minerals by LA-ICP-MS without applying an internal standard. Chemical Geology, 257, 34–43.
Liu, Y.S., Hu, Z.C., Zong, K.Q., Gao, C.G., Gao, S., Xu, J., and Chen, H.H. (2010) Reappraisement and refinement of zircon U-Pb isotope and trace element analyses by LA-ICPMS. Science Bulletin, 55, 1535–1546.
Maeng, M., Lee, H., and Dockko, S. (2013) Phosphate removal using novel combined Fe-Mn-Si oxide adsorbent. Journal of Korean Society of Water and Wastewater, 27, 631–639.
Michael, S., Danuta, K., Yakov, K., and Joörn, B. (2010) Silicon pools and fluxes in soils and landscapes - a review. Journal of Plant Nutrition and Soil Science, 169, 582–582.
Miura, H., Kudou, H., Choi, J.H., and Hariya, Y. (1990) The crystal structure of ramsdellite from Pirika mine. Journal of the Faculty of Science, Hokkaido University, 22, 611–617.
Mohapatra, B.K., Jena, S., Mahanta, K., and Mishra, P. (2008) Goethite morphology and composition in banded iron formation, Orissa, India. Resource Geology, 58, 325–332.
Nahon, D., Beauvais, A., Nziengui-Mapangou, P., and Ducloux, J. (1984) Chemical weathering of Mn-garnets under lateritic conditions in northwest Ivory Coast (West Africa). Chemical Geology, 45, 53–71.
Nambu, M. (1955) Mineralogical study of limonite in Japan. Bulletin of the Research Institute of Mineral Dressing & Metallurgy, Tohoku University, 11, 35–66.
Naslund, H.R., Hughes, J.M., and Birnie, R.W. (1983) Ilvaite, an alteration product replacing olivine in the Skaergaard intrusion. American Mineralogist, 68, 1004–1008.
Neaman, A., Mouélé, F., Trolard, F., and Bourrié G. (2004) Improved methods for selective dissolution of Mn oxides: applications for studying trace element associations. Applied Geochemistry, 19, 973–979.
O’Connor, F., Cheung, W.H., and Valix, M. (2006) Reduction roasting of limonite ores: effect of dehydroxylation. International Journal of Mineral Processing, 80, 88–99.
Okada, K., Hachiya, Y., and Kato, S. (1966) Mineralogical composition of manganiferous limonite from Kuroishi city, Aomori Prefecture. Bulletin of the Research Institute of Mineral Dressing & Metallurgy, Tohoku University, 21, 135–143.
Ostwald, J. (1988) Mineralogy of the Groote Eylandt manganese oxides: a review. Ore Geology Reviews, 4, 3–45.
Pellant, C. (1992) Eyewitness Handbooks: Rocks and Minerals. Dorling Kindersley, UK, 148 pp.
Post, J.E. (1999) Manganese oxide minerals: crystal structures and economic and environmental significance. Proceedings of the National Academy of Sciences, 96, 3447–3454.
Scheinost, A.C., Stanjek, H., Schulze, D.G., Gasser, U., and Sparks, D.L. (2001) Structural environment and oxidation state of Mn in goethite-groutite solid-solutions. American Mineralogist, 86, 139–146.
Sheng, G.Q. and Wang, C.Y. (1989) On the formation condition of the gold in gossans, and prospecting significance in the Tongling mining district, Anhui province. Mineral and Exploration, 6, 22–26 (in Chinese).
Singer, A., Stoffers, P., Heller-Kallai, L., and Szafranek, D. (1984) Nontronite in a deep-sea core from the south pacific. Clays and Clay Minerals, 32, 375–383.
Song, S., Lu, S., and Lopez-Valdivieso, A. (2002) Magnetic separation of hematite and limonite fines as hydrophobic flocs from iron ores. Minerals Engineering, 15, 415–422.
Stone, J.B. (1934) Limonite deposits at the Orient mine, Colorado. Economic Geology, 29, 317–329.
Sun, L. and Chu, Z.C. (2006) Study on geological characteristics, mineralization conditions and assessment criteria of gossan type gold-silver deposits in Anhui province. Geology of Anhui, 16, 94–100 (in Chinese).
Sun, Z., Zhou, H., Glasby, G. P., Yang, Q.H., Yin, X.J., Li, J.W., and Chen, Z.Q. (2012) Formation of Fe-Mn-Si oxide and nontronite deposits in hydrothermal fields on the Valu Fa Ridge, Lau Basin. Journal of Asian Earth Sciences, 43, 64–76.
Taitel-Goldman, N., Ezersky, V., and Mogilyanski, D. (2009) High-resolution transmission electron microscopy study of Fe-Mn oxides in the hydrothermal sediments of the Red Sea Deeps System. Clays and Clay Minerals, 57, 465–475.
Tang, J.A. and Valix, M. (2006) Leaching of low grade limonite and nontronite ores by fungi metabolic acids. Minerals Engineering, 19, 1274–1279.
Tang, W.F. (2000) The Composition and Surface Chemical Characteristics of Fe-Mn Nodules of Several Soils in China. PhD thesis, Huazhong Agricultural University, China, pp. 22–30
Tripathi, J.K. and Rajamani, V. (2007) Geochemistry and origin of ferruginous nodules in weathered granodioritic gneisses, Mysore Plateau, Southern India. Geochimica et Cosmochimica Acta, 71, 1674–1688.
Tsubouchi, N., Mochizuki, Y., Byambajav, E., Takahashi, S., Hanaoka, Y., and Ohtsuka, Y. (2017) Catalytic performance of limonite ores in the decomposition of model compounds of biomass-derived tar. Energy & Fuels, 31, 3893–3904.
Vaasjoki, M. (1985) The teutonic bore deposit, Western Australia: A lead isotope study of an ore and its gossan. Mineralium Deposita, 20, 266–270.
Velasco, F., Herrero, J.M., Suárez, S., Yusta, I., Alvaro, A., and Tornos, F. (2013) Supergene features and evolution of gossans capping massive sulphide deposits in the Iberian Pyrite Belt. Ore Geology Reviews, 53, 181–203.
Wang, X.M., Zhu, M.Q., Lan, S., Ginder-Vogel, M., Liu, F., and Feng, X.H. (2015) Formation and secondary mineralization of ferrihydrite in the presence of silicate and Mn(II). Chemical Geology, 415, 37–46.
Williams, D., Suchowerska, A., and Airey, D. (2012) Limonite - a weathered residual soil heterogeneous at all scales. Geotechnique Letters, 2, 119–122.
Wu, F., Cao, Z., Wang, S., and Zhong, H. (2017) Phase transformation of iron in limonite ore by microwave roasting with addition of alkali lignin and its effects on magnetic separation. Journal of Alloys and Compounds, 722, 651–661.
Xu, W., Ding, X.G., Wu, L.B., Wang, K.Y., and Ding, N. (2011) Metallogenic features and ore prospecting potential at the north rim of the Tongling uplift, Anhui. Geology of Anhui, 21, 138–142 (in Chinese).
Yao, Z.Y., Li, Y., He, J.R., and Sun, N.G. (1992) On study of ore material composition and gold occurrence of gossantype gold deposits from Mid-Lower Reaches of Yangtze River. Volcanology and Mineral Resource, 13, 59–72 (in Chinese).
Yesares, L., Sáez, R., Sel, G.R.D.L., Nieto, J.M., Aiglsperger, T., Proenza, J.A., Domínguez, C.G., and Escobar, J.M. (2015) Gold behavior in supergene profiles under changing redox conditions: the example of the Las Cruces deposit, Iberian pyrite belt. Economic Geology, 110, 2109–2126.
Yesares, L., Sáez, R., Almodívar, G.R.D., Nieto, J.M., Gómez, C., and Ovejero, G. (2017) Mineralogical evolution of the Las Cruces gossan cap (Iberian Pyrite Belt): from subaerial to underground conditions. Ore Geology Reviews, 80, 377–405.
Zhao, X.Y., Ren, J., Cao, J.P., Wei, F., Zhu, C., and Fan, X., et al. (2017) Catalytic reforming of volatiles from biomass pyrolysis for hydrogen-rich gas production over limonite ore. Energy & Fuels, 31, 4054–3060.
Zhao, Y.M., Tan, H.J., Xu, Z.N., Yuan, R.G., Bi, C.S., Zheng, R.L., Li, D.X., and Sun, J.H. (1983) The Calcic-Skarn Iron Ore Deposits of Makeng Type in Southwestern Fujian. Institute of Mineral Deposits, Chinese Academy of Geological Sciences, pp. 40–46.
Zhao, Y.M., Lin, W.W., Bi, C.S., Li, D.X., and Jiang, C.J. (1990) Skarn Deposits of China. Geological Publishing House, Beijing, China, pp. 68–75.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Chen, P., Chen, T., Xie, Q. et al. Mineralogy and Geochemistry of Limonite as a Weathering Product of Ilvaite in the Yeshan Iron Deposit, Tongling, China. Clays Clay Miner. 66, 190–207 (2018). https://doi.org/10.1346/CCMN.2018.064102a
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1346/CCMN.2018.064102a