Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

Abstract Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth’s crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth’s crustal mean of about 1 ppb, compared with 250 times for the next most enriched element. We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases. Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO2, carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ≤10% is leached with the MnO2. Thermodynamic calculations indicate that Te occurs predominantly as H5TeO6− in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO2 in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce.

[1]  R. Gadde,et al.  Heavy metal adsorption by hydrous iron and manganese oxides , 1974 .

[2]  J. Hein,et al.  Two major Cenozoic episodes of phosphogenesis recorded in equatorial Pacific seamount deposits , 1993 .

[3]  A. Koschinsky,et al.  Iron and manganese oxide mineralization in the Pacific , 1997, Geological Society, London, Special Publications.

[4]  L. Cutter,et al.  Sources and cycling of selenium in the western and equatorial Atlantic Ocean , 2001 .

[5]  Yoshimi Suzuki,et al.  Determination of tellurium in sea water. , 1981 .

[6]  M. Bau.  Scavenging of dissolved yttrium and rare earths by precipitating iron oxyhydroxide: experimental evidence for Ce oxidation, Y-Ho fractionation, and lanthanide tetrad effect , 1999 .

[7]  Frank T. Manheim,et al.  Cobalt-Rich Ferromanganese Crusts in the Pacific , 1999 .

[8]  Harold C. Urey,et al.  Abundances of the elements , 1956 .

[9]  J. Hem.  Redox processes at surfaces of manganese oxide and their effects on aqueous metal ions , 1978 .

[10]  P. Halbach,et al.  Mechanisms to explain the platinum concentration in ferromanganese seamount crusts , 1989 .

[11]  P. Huang,et al.  Oxidative power of Mn(IV) and Fe(III) oxides with respect to As(III) in terrestrial and aquatic environments , 1981, Nature.

[12]  A. Tessier,et al.  Speciation and adsorption of arsenic on diagenetic iron oxyhydroxides , 1991 .

[13]  E. Goldberg,et al.  Rare‐Earth distributions in the marine environment , 1963 .

[14]  J. Dillard,et al.  The oxidation states of cobalt and selected metals in Pacific ferromanganese nodules , 1982 .

[15]  J. Hein,et al.  60 Myr records of major elements and Pb–Nd isotopes from hydrogenous ferromanganese crusts: reconstruction of seawater paleochemistry , 1999 .

[16]  B. Pahlavanpour,et al.  The simultaneous determination of arsenic, antimony, bismuth, selenium and tellurium in waters by an inductively coupled plasma/volatile hydride method , 1981 .

[17]  A. Mangini,et al.  Co-fluxes and growth rates in ferromanganese deposits from central Pacific seamount areas , 1983, Nature.

[18]  Nelson Belzile,et al.  Oxidation of antimony (III) by amorphous iron and manganese oxyhydroxides , 2001 .

[19]  M. Nomura,et al.  Direct observation of tetravalent cerium in ferromanganese nodules and crusts by X-ray-absorption near-edge structure (XANES) , 2000 .

[20]  K. Bruland.  Trace elements in seawater. , 1983 .

[21]  F. Morel,et al.  Surface Complexation Modeling: Hydrous Ferric Oxide , 1990 .

[22]  I. Butler,et al.  Trace element distributions in the chalcopyrite wall of a black smoker chimney: insights from laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) , 1999 .

[23]  Li Yuan-hui,et al.  Distribution patterns of the elements in the ocean: A synthesis , 1991 .

[24]  J. Dillard,et al.  The oxidation of cobalt(II) adsorbed on manganese dioxide , 1979 .

[25]  J. Edmond,et al.  Selenium redox chemistry at GEOSECS I re-occupation , 1980 .

[26]  G. Baturin.  The Geochemistry of Manganese and Manganese Nodules in the Ocean , 1987 .

[27]  S. Rossi,et al.  Simultaneous determination of the speciation of selenium and tellurium in geological matrices by use of an iron(III)-modified chelating resin and cathodic stripping voltammetry , 1998 .

[28]  H. Barnes,et al.  Deposition of deep-sea manganese nodules , 1974 .

[29]  Konrad B. Krauskopf,et al.  Introduction to geochemistry , 1967 .

[30]  R. Byrne.  Inorganic speciation of dissolved elements in seawater: the influence of pH on concentration ratios , 2002, Geochemical transactions.

[31]  A. A. Levinson.  INTRODUCTION TO EXPLORATION GEOCHEMISTRY , 1974 .

[32]  W. McDonough,et al.  The composition of the Earth , 1995 .

[33]  R. Parker.  Composition of the Earth's crust , 1967 .

[34]  P. A. Baedecker.  Methods for geochemical analysis , 1987 .

[35]  P. N. Gibson,et al.  X-ray absorption spectroscopy investigation of surface redox transformations of thallium and chromium on colloidal mineral oxides , 1993 .

[36]  J. Mero.  The mineral resources of the sea , 1965 .

[37]  D. Mcphail.  Thermodynamic properties of aqueous tellurium species between 25 and 350 , 1995 .

[38]  C. E. Thompson,et al.  Tellurium Content of Marine Manganese Oxides and Other Manganese Oxides , 1963, Science.

[39]  C. Langmuir,et al.  Cadmium, indium, tin, tellurium, and sulfur in oceanic basalts: Implications for chalcophile element fractionation in the Earth , 2000 .

[40]  K. Nicholson,et al.  Manganese Mineralization: Geochemistry And Mineralogy of Terrestrial And Marine Deposits , 1996 .

[41]  N. Grevesse,et al.  Abundances of the elements: Meteoritic and solar , 1989 .

[42]  J. E. Klovan,et al.  An algorithm andFortran-iv program for large-scaleQ-mode factor analysis and calculation of factor scores , 1971 .

[43]  M. Andreae.  Determination of inorganic tellurium species in natural waters. , 1984, Analytical chemistry.

[44]  A. Koschinsky,et al.  Sequential leaching of marine ferromanganese precipitates: Genetic implications , 1995 .

[45]  R. Reyment,et al.  Statistics and Data Analysis in Geology. , 1988 .

[46]  J. Edmond,et al.  Tellurium species in seawater , 1985, Nature.

[47]  A. Koschinsky,et al.  Uptake of elements from seawater by ferromanganese crusts: solid-phase associations and seawater speciation , 2003 .

[48]  D. S. Cronan,et al.  Handbook of marine mineral deposits , 2000 .