GUAN Yao, SUN Xiaoming, JIANG Xiaodong, SA Rina, ZHOU Li, HUANG Yi, LIU Yating, LI Xiaojie, LU Rongfei, WANG Chi. The effect of Fe-Mn minerals and seawater interface and enrichment mechanism of ore-forming elements of polymetallic crusts and nodules from the South China Sea[J]. Acta Oceanologica Sinica, 2017, 36(6): 34-46. doi: 10.1007/s13131-017-1004-4
Citation: GUAN Yao, SUN Xiaoming, JIANG Xiaodong, SA Rina, ZHOU Li, HUANG Yi, LIU Yating, LI Xiaojie, LU Rongfei, WANG Chi. The effect of Fe-Mn minerals and seawater interface and enrichment mechanism of ore-forming elements of polymetallic crusts and nodules from the South China Sea[J]. Acta Oceanologica Sinica, 2017, 36(6): 34-46. doi: 10.1007/s13131-017-1004-4

The effect of Fe-Mn minerals and seawater interface and enrichment mechanism of ore-forming elements of polymetallic crusts and nodules from the South China Sea

doi: 10.1007/s13131-017-1004-4
  • Received Date: 2016-02-16
  • Rev Recd Date: 2016-04-18
  • Ferromanganese crusts and nodules are important submarine mineral resources that contain various metal elements with significant economic value. In this study, polymetallic crusts and nodules obtained from the South China Sea (SCS) were determined by using X-ray power diffraction (XRD), Raman spectroscopy (RS), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) to systematically investigate and analyze the mineralogical and spectral characteristics of the Fe-Mn minerals. XRD measurements revealed that the SCS polymetallic crusts and nodules were composed of vernadite, quartz, and plagioclase. The nodules also contained todorokite. The Fe-phase minerals of the SCS crusts and nodules were composed of amorphous Fe oxide/hydroxide, and the Mn-and Fe-phases minerals exhibited relatively poor degrees of crystallization. FTIR results showed that the Fe-Mn minerals in the crusts and nodules included a large number of surface hydroxyl groups. These surface hydroxyl groups contained protons that could provide reactive sites for complexation of ore-forming elements in seawater. XPS results indicated that the surfaces of the Fe-Mn minerals mainly contained Fe, Mn, and O. Fe was present in the trivalent oxidation state, while Mn, which may contain several bivalent oxidation state, was present in the tetravalent and trivalent oxidation states. The SCS polymetallic crusts and nodules were compared with Pacific seamount crusts, and results showed that the surface hydroxyl (-OH) groups of the SCS crusts and nodules numbered more than the lattice oxygen (O2-). But the lattice oxygen of Pacific seamount crusts numbered more than the surface hydroxyl groups. This characteristic indicated that the degree of crystallization of Fe-Mn minerals from the Pacific Ocean was higher than that of minerals from the South China Sea. Comprehensive studies showed that ore-forming elements in the interface between seawater and the Fe-Mn minerals in the submarine ferromanganese crusts and nodules employed the following enrichment mechanisms:(1) the metal ion complexed with the surface hydroxyl of Fe-Mn minerals to form hydroxyl complexes, which were connected by coordination bonds or stable inner-sphere complexes that exchanged protons on the mineral surfaces; (2) the charged surfaces of the minerals and metal cations formed outer-sphere complexes, which made up the electrostatic double layer, through electrostatic adsorption; and (3) the metal cations isomorphously exchanged the Mn and Fe ions of the mineral lattice structure.
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  • Bau M, Koschinsky A, Dulski P, et al. 1996. Comparison of the partitioning behaviours of yttrium, rare earth elements, and titanium between hydrogenetic marine ferromanganese crusts and seawater. Geochimica et Cosmochimica Acta, 60(10):1709-1725
    Bidoglio G, Gibson P N, O'Gorman M, et al. 1993. X-ray absorption spectroscopy investigation of surface redox transformations of thallium and chromium on colloidal mineral oxides. Geochimica et Cosmochimica Acta, 57(10):2389-2394
    Burns R G. 1976. The uptake of cobalt into ferromanganese nodules, soils, and synthetic manganese (IV) oxides. Geochimica et Cosmochimica Acta, 40(1):95-102
    Cao Lixin, Wan Haibao, Wang Shubin, et al. 1999. The effect of surface structure on the photoluminescence of SnO2 nanoparticles in hydrosols and organosols. Spectroscopy and Spectral Analysis (in Chinese), 19(5):651-654
    Chukhrov F V, Gorshkov A I, Sivtsov A V, et al. 1979. New data on natural todorokites. Nature, 278(5705):631-632
    Davis J A, Kent D B. 1990. Surface complexation modeling in aqueous geochemistry. In:Hochella Jr M F, White A F, eds. Mineral-water Interface Geochemistry:Reviews in Mineralogy, Volume 23. Washington D C:Mineralogical Society of America, 177-260
    Drits V A, Silvester E, Gorshkov A I, et al. 1997. Structure of synthetic monoclinic Na-rich birnessite and hexagonal birnessite:I. results from X-ray diffraction and selected-area electron diffraction. American Mineralogist, 82(9-10):946-961
    Dzombak D A, Morel F M M. 1990. Surface Complexation Modeling:Hydrous Ferric Oxide. New York:Wiley, 81-95
    Farley K J, Dzombak D A, Morel F M M. 1985. A surface precipitation model for the sorption of cations on metal oxides. Journal of Colloid and Interface Science, 106(1):226-242
    Feng Qi, Kanoh H, Miyai Y, et al. 1995. Alkali metal ions insertion/extraction reactions with hollandite-type manganese oxide in the aqueous phase. Chemistry of Materials, 7(1):148-153
    Feng Qi, Kanoh H, Ooi K. 1999. Manganese oxide porous crystals. Journal of Materials Chemistry, 9(2):319-333
    Feng Xionghan. 2004. Syntheses, transformations and surface chemistry characteristics of the common manganese oxide minerals in soils (in Chinese)[dissertation]. Wuhan:Huazhong Agricultural University
    Friedrich G, Schmitz-Wiechowski A. 1980. Mineralogy and chemistry of a ferromanganese crust from a deep-sea hill, central Pacific, “Valdivia” cruise VA 132. Marine Geology, 37(1-2):71-90
    Garvie L A J, Craven A J. 1994. High-resolution parallel electron energy-loss spectroscopy of Mn L2, 3-edges in inorganic manganese compounds. Physics and Chemistry of Minerals, 21(4):191-206
    Golden D C, Chen C C, Dixon J B. 1987. Transformation of birnessite to buserite, todorokite, and manganite under mild hydrothermal treatment. Clays and Clay Minerals, 35(4):271-280
    Guan Yao, Sun Xiaoming, Shi Guiyong, et al. 2017. Rare earth elements (REE) composition and constraints on the genesis of the polymetallic crusts and nodules in the South China Sea. Acta Geologica Sinica (English Edition) (in press)
    Halbach P, Kriete C, Prause B, et al. 1989. Mechanisms to explain the platinum concentration in ferromanganese seamount crusts. Chemical Geology, 76(1-2):95-106
    He Gaowen, Ma Weilin, Song Chengbing, et al. 2011a. Distribution characteristics of seamount cobalt-rich ferromanganese crusts and the determination of the size of areas for exploration and exploitation. Acta Oceanologica Sinica, 30(3):63-75
    He Gaowen, Sun Xiaoming, Xue Ting. 2011b. A Comparative Study of the Geology, Geochemistry and Metallogenetic Mechanism of Polymetallic Nodules and Cobalt-rich Crusts from the Pacific Ocean (in Chinese). Beijing:Geological Publishing House
    Hein J R, Koschinsky A. 2014. Deep-ocean ferromanganese crusts and nodules. In:Holland H D, Turekian K K, eds. Treatise on Geochemistry. 2nd ed. Amsterdam:Elsevier, 273-291
    Hein J R, Koschinsky A, Bau M, et al. 2000. Cobalt-rich ferromanganese crusts in the Pacific. In:Cronan D S, ed. Handbook of Marine Mineral Deposits. Boca Raton:CRC Press, 239-279
    Hein J R, Koschinsky A, Halliday A N. 2003. Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium. Geochimica et Cosmochimica Acta, 67(6):1117-1127
    Hein J R, Spinardi F, Okamoto N, et al. 2015. Critical metals in manganese nodules from the Cook Islands EEZ, abundances and distributions. Ore Geology Reviews, 68:97-116
    Hiemstra T, De Wit J C M, Van Riemsdijk W H. 1989a. Multisite proton adsorption modeling at the solid/solution interface of (hydr)oxides:a new approach, 2. Application to various important (hydr)oxides. Journal of Colloid and Interface Science, 133(1):105-117
    Hiemstra T, Van Riemsdijk W H, Bolt G H. 1989b. Multisite proton adsorption modeling at the solid/solution interface of (hydr)oxides:a new approach:I. Model description and evaluation of intrinsic reaction constants. Journal of Colloid and Interface Science, 133(1):91-104
    Hochella Jr M F. 1990. Atomic structure, microtopography, composition, and reactivity of mineral surfaces. In:Hochella Jr M F, White A F, eds. Mineral-water Interface Geochemistry:Reviews in Mineralogy, v 23. Washington D C:Mineralogical Society of America, 87-132
    Jiang Xuejun, Lin Xuehui, Yao De, et al. 2011. Enrichment mechanisms of rare earth elements in marine hydrogenic ferromanganese crusts. Science China:Earth Sciences, 54(2):197-203
    Kashiwabara T, Takahashi Y, Marcus M A, et al. 2013. Tungsten species in natural ferromanganese oxides related to its different behavior from molybdenum in oxic ocean. Geochimica et Cosmochimica Acta, 106:364-378
    Kashiwabara T, Takahashi Y, Tanimizu M. 2009. A XAFS study on the mechanism of isotopic fractionation of molybdenum during its adsorption on ferromanganese oxides. Geochemical Journal, 43(6):e31–e36
    Kashiwabara T, Takahashi Y, Tanimizu M, et al. 2011. Molecular-scale mechanisms of distribution and isotopic fractionation of molybdenum between seawater and ferromanganese oxides. Geochimica et Cosmochimica Acta, 75(19):5762-5784
    Kloprogge J T, Duong L V, Wood B J, et al. 2006. XPS study of the major minerals in bauxite:gibbsite, bayerite and (pseudo-) boehmite. Journal of Colloid and Interface Science, 296(2):572-576
    Knipe S W, Mycroft J R, Pratt A R, et al. 1995. X-ray photoelectron spectroscopic study of water adsorption on iron sulphide minerals. Geochimica et Cosmochimica Acta, 59(6):1079-1090
    Koschinsky A, Halbach P. 1995. Sequential leaching of marine ferromanganese precipitates:genetic implications. Geochimica et Cosmochimica Acta, 59(24):5113-5132
    Koschinsky A, Hein J R. 2003. Uptake of elements from seawater by ferromanganese crusts:solid-phase associations and seawater speciation. Marine Geology, 198(3-4):331-351
    Koschinsky A, Winkler A, Fritsche U. 2003. Importance of different types of marine particles for the scavenging of heavy metals in the deep-sea bottom water. Applied Geochemistry, 18(5):693-710
    Kuhn T, Bau M, Blum N, et al. 1998. Origin of negative Ce anomalies in mixed hydrothermal-hydrogenetic Fe-Mn crusts from the Central Indian Ridge. Earth and Planetary Science Letters, 163(1-4):207-220
    Liao Shuijiao, Wang Juan, Zhu Duanwei, et al. 2006. Structural characteristics of goethite and its B-loaded oxides. Acta Pedologica Sinica (in Chinese), 43(5):742-748
    Little S H, Sherman D M, Vance D, et al. 2014. Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts. Earth and Planetary Science Letters, 396:213-222
    Liu Chongxuan, Kota S, Zachara J M, et al. 2001. Kinetic analysis of the bacterial reduction of goethite. Environmental Science & Technology, 35(12):2482-2490
    Liu Ruiping, Liu Huijuan, Qiang Zhimin, et al. 2009. Effects of calcium ions on surface characteristics and adsorptive properties of hydrous manganese dioxide. Journal of Colloid and Interface Science, 331(2):275-280
    Manceau A, Charlet L. 1992. X-ray absorption spectroscopic study of the sorption of Cr(Ⅲ) at the oxide-water interface:I. Molecular mechanism of Cr(Ⅲ) oxidation on Mn oxides. Journal of Colloid and Interface Science, 148(2):425-442
    Manceau A, Gorshkov A I, Drits V A. 1992. Structural chemistry of Mn, Fe, Co, and Ni in manganese hydrous oxides:Part Ⅱ. Information from EXAFS spectroscopy and electron and X-ray diffraction. American Mineralogist, 77:1144-1157
    Mathieu H J, Landolt D. 1986. An investigation of thin oxide films thermally grown in situ on Fe-24Cr and Fe-24Cr-11Mo by auger electron spectroscopy and X-ray photoelectron spectroscopy. Corrosion Science, 26(7):547-559
    Mellin T A, Lei Guobin. 1993. Stabilization of 10Å-manganates by interlayer cations and hydrothermal treatment:implications for the mineralogy of marine manganese concretions. Marine Geology, 115(1-2):67-83
    Mitsunobu S, Harada T, Takahashi Y. 2006. Comparison of antimony behavior with that of arsenic under various soil redox conditions. Environmental Science & Technology, 40(23):7270-7276
    Moffett J W, Ho J. 1996. Oxidation of cobalt and manganese in seawater via a common microbially catalyzed pathway. Geochimica et Cosmochimica Acta, 60(18):3415-3424
    Motschi H. 1987. Aspects of the molecular structure in surface complexes:spectroscopic investigations. In:Stumm W, ed. Aquatic Surface Chemistry. New York:John Wiley and Sons, 111-126
    Murray J W, Dillard J G. 1979. The oxidation of cobalt(Ⅱ) adsorbed on manganese dioxide. Geochimica et Cosmochimica Acta, 43(5):781-788
    Naidja A, Liu C, Huang P M. 2002. Formation of protein-birnessite complex:XRD, FTIR, and AFM analysis. Journal of Colloid and Interface Science, 251(1):46-56
    Nakamoto K. 1978. Infrared and Raman Spectra of Inorganic and Coordination Compounds. 3rd ed. New York:John Wiley, 324-330
    Parida K M, Mohanty S. 1998. Studies on Indian Ocean manganese nodules:VⅢ. Adsorption of aqueous phosphate on ferromanganese nodules. Journal of Colloid and Interface Science, 199(1):22-27
    Potter R M, Rossman G R. 1979. The tetravalent manganese oxides:identification, hydration, and structural relationships by infrared spectroscopy. American Mineralogist, 64:1199-1218
    Pratt A R, Muir I J, Nesbitt H W. 1994. X-ray photoelectron and Auger electron spectroscopic studies of pyrrhotite and mechanism of air oxidation. Geochimica et Cosmochimica Acta, 58(2):827-841
    Russell J D. 1979. Infrared spectroscopy of ferrihydrite:evidence for the presence of structural hydroxyl groups. Clay Minerals, 14(2):109-114
    Shi Nicheng, Ma Zhesheng, He Wanzhong, et al. 1995. Nano-solids in manganese nodules from northern part of Pacific Ocean floor-Nano-solids in minerals and prospects of its uses in industry. Science in China Series B:Chemistry, 38(12):1493-1500
    Singh B, Sherman D M, Gilkes R J, et al. 2000. Structural chemistry of Fe, Mn, and Ni in synthetic hematites as determined by extended X-ray absorption fine structure spectroscopy. Clays and Clay Minerals, 48(5):521-527
    Sposito G. 1984. The Surface Chemistry of Soils. New York:Oxford University Press
    Stumm W. 1992. Chemistry of the Solid-water Interface:Processes at the Mineral-water and Particle-water Interface in Natural Systems. New York:John Wiley and Sons
    Stumm W, Morgan J J. 1996. Aquatic Chemistry. New York:John Wiley and Sons
    Tamura H, Mita K, Tanaka A, et al. 2001. Mechanism of hydroxylation of metal oxide surfaces. Journal of Colloid and Interface Science, 243(1):202-207
    Tan B J, Klabunde K J, Sherwood P M A. 1991. XPS studies of solvated metal atom dispersed (SMAD) catalysts. Evidence for layered cobalt-manganese particles on alumina and silica. Journal of the American Chemical Society, 113(3):855-861
    Tonkin J W, Balistrieri L S, Murray J W. 2004. Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model. Applied Geochemistry, 19(1):29-53
    Wang Yifeng, Bryan C, Xu Huifang, et al. 2003. Nanogeochemistry:geochemical reactions and mass transfers in nanopores. Geology, 31(5):387-390
    Wei Junfeng, Wu Daqing. 2000. Surface ionization and surface complexation models at mineral/water interface. Advance in Earth Sciences (in Chinese), 15(1):90-96
    Xiong Yi, Chen Jiafang. 1990. Soil Colloid (Part Ⅲ):Properties of Soil Colloid (in Chinese). Beijing:Science Press
    Xue Ting. 2007. Geochemical characters and ore-forming elements enrichment mechanism of ferromanganese crusts from Pacific Ocean (in Chinese)[dissertation]. Guangzhou:Sun Yat-sen University
    Yao Wensheng, Millero F J. 1996. Adsorption of phosphate on manganese dioxide in seawater. Environmental Science & Technology, 30(2):536-541.
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