Oxidation of Mn(II): Initial mineralogy,oxidation state and ageing     

James W Murray  John G Dillard  Rudolf Giovanoli  Harald Moers  Werner Stumm 《Geochimica et cosmochimica acta》1985,49(2):463-470

The initial solid phase oxidation products formed during the oxidation of aqueous Mn(II) at 25°C were studied as a function of time. The analyses included morphology (TEM), mineralogy (x-ray diffraction), $\text{O}\text{Mn}$ ratio (iodometric method), oxidation state of manganese (XPS), and dissolved manganese. The initial solid formed under our conditions was Mn₃O₄ (hausmannite) which converted completely to γMnOOH (manganite) after eight months. βMnOOH (feitknechtite) appeared to be an intermediate in this transformation. The $\text{O}\text{Mn}$ ratio was initially 1.37 and increased to 1.49 over the same time span. Throughout the course of this study the XPS analyses showed that the surface of the solids (<50 Å) was dominated by Mn(III). The solution pH and dissolved manganese concentrations were consistent with disproportionation and oxidation reactions that favor the transformation of Mn₃O₄ to γMnOOH but not to γMnO₂.  相似文献   

Rare earth element zonation in Pacific ferromanganese nodules   总被引：1，自引：0，他引：1  

H. Elderfield  C.J. Hawkesworth  M.J. Greaves  S.E. Calvert 《Geochimica et cosmochimica acta》1981,45(7):1231-1234

The lower surfaces of ferromanganese nodules from the north equatorial Pacific Ocean, which are enriched in Mn, Cu and Ni, and the upper surfaces, which are enriched in Fe, P and Co, have been analyzed for La, Ce, Nd, Sm, Eu, Gd, Dy, Er and Yb. The REE contents are lower and the Ce anomaly is smaller in the lower surfaces than in the upper surfaces. The magnitude of the Ce anomaly increases with decreasing $\text{Mn}\text{Fe}$ ratio, indicative of a seawater origin. The zonal distribution of the other REE supports the conclusion derived previously from inter-nodule and nodule/sediment relationships that diagenetic fixation of rare earths in sediments affects their enrichment by nodular iron oxyhydroxides.  相似文献   

Manganese carbonate overgrowths on foraminifera tests     

Edward A. Boyle 《Geochimica et cosmochimica acta》1983,47(10):1815-1819

Below the zone where manganese is remobilized as Mn²⁺(aq), reductively cleaned foraminifera in deep sea sediments have much higher $\text{Mn}\text{Ca}$ than those in core tops and sediment traps. $\text{Mn}\text{Ca}$ ranges from less than 20 × 10^?6 in and above the MnO₂ maximum to as high as 700 × 10^?6 in reducing Panama Basin sediments. The most plausible explanation for this enrichment is that the tests are coated with Mn carbonate overgrowths. These coatings can account for a significant proportion of the Mn in reduced deep-sea sediments. Uptake of manganous ion by carbonate may explain the absence of Mn nodules in areas of high carbonate accumulation. Extreme degrees of overgrowth can alter foram trace element values, but this artifact can be avoided by avoiding foraminifera with high Mn/Ca.  相似文献   

Ferromanganese oxide deposits from the Central Pacific Ocean,I. Encrustations from the Line Islands Archipelago     

Andrew C Aplin  David S Cronan 《Geochimica et cosmochimica acta》1985,49(2):427-436

Chemical and mineralogical analyses of a well-controlled suite of ferromanganese encrustations from the Line Islands Archipelago (Central Pacific) suggest that they represent purely hydrogenous deposits—i.e. they have formed through the slow accumulation of trace metal-enriched oxides directly from the water-column. Mineralogically they consist predominantly of δMnO₂ and amorphous FeOOHxH₂O. Compositionally, they are similar to δMnO₂ nodules from adjoining basinal areas but are enriched in both Mn (mean = 20.4%, max = 29.3%) and Co (mean = 0.55%, max = 1.57%). δMnO₂ is the most important trace metal bearing phase; strong associations are noted between it and Co, Mo, Ni, Zn, and Cd, whilst only Be is associated specifically with FeOOH. V, Sr and Pb are partitioned between the authigenic oxide phases, whilst Ti most probably occurs as TiO₂xH₂O. Cu is contained in both aluminosilicate contaminant phases and Fe oxide phases. These relations are considered to reflect the differing scavenging behaviour of Mn and Fe oxides in the water column.Crusts from ~1–2 km are enriched in Mn and the Mn-related elements and exhibit higher $\text{Mn}\text{Fe}$ ratios than deeper crusts, which are compositionally constant. The higher $\text{Mn}\text{Fe}$ ratios may result from a supply of Mn from continental borderland sediments at these depths, which is transported horizontally by advective-diffusive processes. Since manganophile elements are enriched relative to Mn in the 1–2 km crusts, it is considered that the supply of Mn is scavenged by existing oxides, is oxidised and effectively occludes them. A higher proportion of oxide particles thus exhibit Mn oxide scavenging properties in the 1–2 km depth zone. The increased vertical flux of Mn resulting from the supply at ~1–2 km is not reflected by higher $\text{Mn}\text{Fe}$ ratios in deeper crusts, so that the vertical flux of oxides is not simply related to the standing crop. The $\text{Mn}\text{Fe}$ ratios of the crusts thus reflect the composition of suspended oxides at similar depths.  相似文献   

Rare earth element geochemistry of oceanic ferromanganese nodules and associated sediments     

H Elderfield  C.J Hawkesworth  M.J Greaves  S.E Calvert 《Geochimica et cosmochimica acta》1981,45(4):513-528

Analyses have been made of REE contents of a well-characterized suite of deep-sea (> 4000 m.) principally todorokite-bearing ferromanganese nodules and associated sediments from the Pacific Ocean. REE in nodules and their sediments are closely related: nodules with the largest positive Ce anomalies are found on sediments with the smallest negative Ce anomalies; in contrast, nodules with the highest contents of other rare earths (3 + REE) are found on sediments with the lowest 3 + REE contents and vice versa. ${}^{143}\text{Nd}{}^{144}\text{Nd}$ ratios in the nodules (～0.51244) point to an original seawater source but an identical ratio for sediments in combination with the REE patterns suggests that diagenetic reactions may transfer elements into the nodules. Analysis of biogenic phases shows that the direct contribution of plankton and carbonate and siliceous skeletal materials to REE contents of nodules and sediments is negligible. Inter-element relationships and leaching tests suggest that REE contents are controlled by a P-rich phase with a REE pattern similar to that for biogenous apatite and an Fe-rich phase with a pattern the mirror image of that for sea water. It is proposed that 3 + REE concentrations are controlled by the surface chemistry of these phases during diagenetic reactions which vary with sediment accumulation rate. Processes which favour the enrichment of transition metals in equatorial Pacific nodules favour the depletion of 3 + REE in nodules and enrichment of 3 + REE in associated sediments. In contrast, Ce appears to be added both to nodules and sediments directly from seawater and is not involved in diagenetic reactions.  相似文献   

Oxidation state of marine manganese nodules     

D.Z. Piper  J.R. Basler  J.L. Bischoff 《Geochimica et cosmochimica acta》1984,48(11):2347-2355

Analyses of the bulk oxidation state of marine manganese nodules indicates that more than 98% of the Mn in deep ocean nodules is present as Mn(IV). The samples were collected from three quite different areas: the hemipelagic environment of the Guatemala Basin, the pelagic area of the North Pacific, and seamounts in the central Pacific. Results of the study suggest that todorokite in marine nodules is fully oxidized and has the following stoichiometry: (K, Na, Ca, Ba)_.33(Mg, Cu, Ni)_.76Mn₅O₂₂(H₂O)_3.2.  相似文献   

Ferromanganese nodules from MANOP Sites H,S, and R—Control of mineralogical and chemical composition by multiple accretionary processes   总被引：3，自引：0，他引：3  

Jack Dymond  Mitchell Lyle  Bruce Finney  David Z. Piper  Kim Murphy  Roberta Conard  Nicklas Pisias 《Geochimica et cosmochimica acta》1984,48(5):931-949

  相似文献   

The formation of todorokite and birnessite in sea water pumped from under ground     

N Takematsu  Y Sato  S Okabe 《Geochimica et cosmochimica acta》1984,48(5):1099-1106

Manganese oxides precipitated from aerated well sea water at the Marine Science Museum, Tokai University, have been analyzed chemically and mineralogically. The $\text{O}\text{Mn}$ ratios are lower in todorokite than in birnessite but these minerals have similar contents of minor transition metals, which can be taken up additionally from sea water after the precipitation of Mn oxides. On the basis of these results, the genesis of Mn minerals is discussed in relation to marine Mn nodules.  相似文献   

Oxygen consumption rates in pelagic sediments from the Central Pacific: First estimates from microelectrode profiles     

Clare E Reimers  Susan Kalhorn  Steven R Emerson  Kenneth H Nealson 《Geochimica et cosmochimica acta》1984,48(5):903-910

Oxygen profiles in pelagic sediments from the Manganese Nodule Program calcareous and siliceous ooze sites (MANOP sites C and S) in the central Pacific Ocean were measured with microelectrodes and are used to predict oxygen consumption rates beneath the sediment-water interface. We explain possible artifacts which occur during sample recovery and argue that minimum estimates of 0.083 and 0.025 μ moles $\text{O}{}_2\text{cm}{}^2\text{day}$ (C and S, respectively) can be calculated from the data. These oxygen consumption rates are in good agreement with in situ respirometer measurements previously reported for comparable sediments in the north Pacific, but previous estimates based on modeling of pore water nitrate profiles at both sites are two to five times smaller than our minimum fluxes. The differences in oxygen fluxes calculated by the two methods are probably in part due to uncertainty in the assumptions inherent in the nitrate model. However, non-steady state fluctuations in particulate organic matter fluxes could also be a reason for the disparity.  相似文献   

Geochemistry of the Manganese Ore Process in the Ocean: Evidence from Rare Earth Elements     

Dubinin  A. V.  Sval'nov  V. N. 《Lithology and Mineral Resources》2003,38(2):91-100

Processes governing the formation of rare earth elements (REE) composition are considered for ferromanganese deposits (nodules, separate parts of nodules, and micronodules of different fractions) within the Clarion–Clipperton ore province in the Pacific Ocean. It is shown that ferromanganese oxyhydroxide deposits with different chemical compositions can be produced in sediments under similar sedimentation conditions. In areas with high bioproductivity, the size of micronodules has a positive correlation with the Mn content and Mn/Fe and P/Fe ratios and a negative correlation with Fe, P, REE, and Ce anomaly. The behavior of REE in micronodules from sediments within bioproductive zones is related to increase of the influence of diagenetic processes in sediments as a response to the growth of the size of micronodules. Distinctions in the chemical composition of micronodules and nodules are related to their interrelations with associated sediments. Micronodules grow in sediments using hydrogenous ferromanganese oxyhydroxides. As they grow, micronodules are enriched in the labile fraction of sediments reworked during diagenesis. Sources of the material of ferromanganese nodules are governed by their formation at the water bottom interface. Their upper part is formed by direct settling of iron oxyhydroxides from the bottom water, whereas the lower part is accumulated due to diagenetic processes in sediments. Differences of REE compositions in ferromanganese deposits are caused by the reduction of manganese during diagenesis and its separation from iron. Iron oxyhydroxides form a sorption complex due to the sorption of phosphate-ion from bottom and pore waters. The sorption of phosphate-ion results in an additional sorption of REE.  相似文献   

Uranium in pacific deep-sea sediments and manganese nodules     

H. Kunzendorf  W.L. Pluger  G.H. Friedrich 《Journal of Geochemical Exploration》1983,19(1-3)

A total of 1344 manganese nodules and 187 pelagic sediments from 9 areas in the North and the South Pacific were analyzed for U by the delayed-neutron counting technique. A strong positive correlation between U and Fe in nodules and sediments suggests a co-precipitative removal from sea water into the Fe-rich ferromanganese mineral phase δ -MnO₂. Enrichment of U and Fe in nodules from the northwestern slopes of two submarine hills (U between 6 and 9 ppm) in the equatorial nodule belt is thought to be caused by directional bottom water flow creating elevated oxygenized conditions in areas opposed to the flow. Economically important nodule deposits from the nodule belt and the Peru Basin have generally low U contents, between 3 and 5 ppm. Insignificant resources of U of about 4 × 10⁵ in the Pacific manganese nodules are estimated.  相似文献   

Thorium and radium isotopic relationships in manganese nodules and sediments at MANOP Site S     

Willard S Moore 《Geochimica et cosmochimica acta》1984,48(5):987-992

Relationships among Th and Ra isotopes in nodule, sediment and water phases at MANOP Site S establish the most likely source for Th in the nodules, the frequency of nodule turning, and the similarity of micro and macro nodules. Manganese nodules and bottom waters have ${}^{230}\text{Th}{}^{232}\text{Th}$ activity ratios considerably higher than other phases at this site suggesting that sea water is the likely source of Th for the nodules. Similar ${}^{230}\text{Th}{}^{232}\text{Th}$ activity ratios in nodule tops and bottoms and in certain cases departure from expected ${}^{226}\text{Ra}{}^{230}\text{Th}$ activity ratios in nodule tops and bottoms indicate that the nodules rotate every one to ten thousand years. The micro nodules have diffusion coefficients of Ra similar to macro nodule bottoms. I suggest that they may act as a carrier phase for transporting metals through oxic sediments to nodules.  相似文献   

Comparison of elemental accumulation rates between ferromanganese deposits and sediments in the South Pacific Ocean     

Tom Kraemer  James C. Schornick 《Chemical Geology》1974,13(3):187-196

Rates of accumulation of Fe and Mn, as well as Cu, Ni, Co, Pb, Zn, Hg, U and Th have been determined for five ferromanganese deposits from four localities in the South Pacific Ocean.Manganese is accumulating in nodules and crusts at a rate roughly equivalent to that found to be accumulating in sediments in the same area. Iron shows a deficiency in accumulation in nodules and crusts with respect to sediments, especially near the continents, but also in the central and south-central Pacific. Copper is accumulating in nodules and crusts at a rate one order of magnitude less than the surrounding sediments.This is interpreted as meaning that most of the Mn is supplied as an authigenic phase to both sediments and nodules while Fe is supplied mostly by ferromanganese micro-nodules and by detrital and adsorbed components of sediments; and Cu is enriched in sediments relative to nodules and crusts most probably through biological activity.  相似文献   

Geochemistry of rare earth elements in bottom sediments of the Brazil Basin, Atlantic Ocean     

A. V. Dubinin  M. N. Rimskaya-Korsakova 《Lithology and Mineral Resources》2011,46(1):1-16

The sedimentation and ore formation were studied in sediments from nine stations located in the 24°W profile in the Brazil Basin of the Atlantic Ocean. The sediments are represented by mio- and hemipelagic muds, which are variably enriched in hydrothermal iron and manganese oxyhydroxides. As compared to the sediments from other basins of the Atlantic Ocean, these rocks are marked by extremely high manganese contents (up to 1.33%) and maximal enrichment in Ce. It was shown that the positive Ce anomaly is related to the REE accumulation on iron oxyhydroxides. Influence of hydrothermal source leads to the decrease of Ce anomaly and LREE/HREE ratio. In the reduced sediments, preservation of positive Ce anomaly and/or its disappearance was observed after iron and manganese reduction. The REE contents were determined for the first time in the Ethmodiscus oozes of the Brazil Basin. Ore deposits of the Brazil Basin are represented by ferromanganese crust and ferromanganese nodules. Judging from the contents of iron, manganese, rare, and trace elements, these formations are ascribed to the sedimentation (hydrogenic) deposits. They are characterized by a notable positive Ce anomaly in the REE pattern. The extremely high Ce content (up to 96% of total REE) was discovered for the first time in the buried nodules (Mn/Fe = 0.88).  相似文献   

Transport and release of transition elements during early diagenesis: Sequential leaching of sediments from MANOP Sites M and H. Part I. pH 5 acetic acid leach     

Mitchell Lyle  G.Ross Heath  James M. Robbins 《Geochimica et cosmochimica acta》1984,48(9):1705-1715

Sediments from MANOP sites M and H in the eastern tropical Pacific Ocean can be partitioned into operationally defined phases by means of a sequential leach procedure. This paper reports the results of the first leach in the sequence, an acetic acid solution buffered as p H 5 with sodium acetate. This leach is designed to remove carbonate-bound and sorbed cations. The only cation bound in a consistent ratio to calcium in the carbonate is strontium. The molar ratio is 2 × 10^?3. In contrast, transition metals are sorbed onto the surfaces of other sedimentary particles. The proportions sorbed range from 2 to 10% of the total manganese, about 10% of the total nickel and copper, and less than 1% of the total iron. The pool of sorbed metals in surface sediments is sufficiently large and the rate of biological stirring is sufficiently rapid for this metal reservoir potentially to dominate the porewater reservoir in supplying metals to ferromanganese nodules. A simple model for nodule growth based upon transfer of metals through this reservoir suggests that only 1% of the sedimentary sorbed metals within a radius of 2 to 9 cm is required to support typical nodule growth rates.  相似文献   

Ferromanganese oxide deposits from the Central Pacific Ocean,II. Nodules and associated sediments   总被引：1，自引：0，他引：1  

Andrew C. Aplin  David S. Cronan 《Geochimica et cosmochimica acta》1985,49(2):437-451

Bulk chemical, mineralogical and selective leach analyses have been made on a suite of abyssal ferromanganese nodules and associated sediments from the S.W. equatorial Pacific Ocean. Compositional relations between nodules, sediment oxyhydroxides and nearby ferromanganese encrustations are drawn assuming that the crusts represent purely hydrogenetic ferromanganese material. Crusts, δMnO₂-rich nodules and sediment oxyhydroxides are compositionally similar and distinct from diagenetic todorokitebearing nodules. Compared to Fe-Mn crusts, sediment oxyhydroxides are however slightly enriched, relative to Mn and Ni, in Fe, Cu, Zn, Ti and Al, and depleted in Co and Pb, reflecting processes of non-hydrogenous element supply and diagenesis. δMnO₂ nodules exhibit compositions intermediate between Fe-Mn crusts and sediment oxyhydroxides and thus are considered to accrete oxides from both the water column and associated sediments.Deep ocean vertical element fluxes associated with large organic aggregates, biogenic calcite, silica and soft parts have been calculated for the study area. Fluxes associated with organic aggregates are one to three orders of magnitude greater than those associated with the other phases considered, are in good agreement with element accumulation rates in sediments, and are up to four orders of magnitude greater than element accumulation rates in nodules. Metal release from labile biogenic material in surface sediments can qualitatively explain the differences between the composition of Fe-Mn crusts and sediment oxyhydroxides.Todorokite-rich diagenetic nodules are confined to an eastwards widening equatorial wedge. It is proposed that todorokite precipitates directly from interstitial waters. Since the transition metal chemistry of interstitial waters is controlled dominantly by reactions involving the breakdown of organic carbon, the supply and degradation rate of organic material is a critical factor in the formation of diagenetic nodules. The wide range of (trace metal/Mn) ratios observed in marine todorokite reflects a balance between the release of trace metals from labile biogenic phases and the reductive remobilisation of Mn oxide, both of which are related to the breakdown of organic carbon.  相似文献   

Growth of a manganese nodule from Peru Basin: A radiochemical anatomy     

J.L Reyss  N Lemaitre  T.L Ku  V Marchig  J.R Southon  D.E Nelson  J.S Vogel 《Geochimica et cosmochimica acta》1985,49(11):2401-2408

Attempts have been made to study the entire growth history of a manganese nodule from the northern part of Peru Basin in the Pacific using radiochemical profiles of ${}^{230}\text{Th}{}^{232}\text{Th}$, ${}^{227}\text{Th}{}^{230}\text{Th}$, and ${}^{10}\text{Be}{}^9\text{Be}$. Combined with the observations on Fe-Mn contents and textural variation, the radiochemical data indicate that the nodule grew more or less concentrically throughout most of its existence since it formed 1.5 my ago, receiving Mn from both bottom water and pore water. This condition appeared to have changed about 180 ky ago when the growth became asymmetric in that the top and bottom sides became fixed in their relative positions on the sea floor. Since then, the bottom side accreted with a fast rate of close to 200 mm/my, apparently fueled by the supply of diagenetically remobilized Mn in pore water from the sediment substrate. In the meantime, the top side accumulated at about 6 mm/my, a value which is in the normal range for deep-sea nodules having their Mn supplied from the hydrogenous source.  相似文献   

Rare earth elements in ferromanganese nodules and other marine phases   总被引：1，自引：0，他引：1  

David Z. Piper 《Geochimica et cosmochimica acta》1974,38(7):1007-1022

The concentrations of rare-earth elements (REE) have been measured in 31 ferromanganese nodules from the Pacific and Indian Oceans and vary by almost a factor of 5. Too few nodules have been analyzed to define possible regional trends. The shale-normalized patterns, however, permit division of nodules into two groups: those from depth greater than 3000–3500 m and those from less depth. The factors that determine this change in the relative concentration of REE may be related to the mineralogy of manganese phases and/or the transport of REE to the deep ocean by particulate matter.Comparison of the REE patterns of nodules with those of phillipsite, phosphorite, clays, CaCO₃ and seawater suggests that the patterns of these phases reflect fractionation from an initial pattern closely resembling that of shale. By assuming that the accumulation rate of REE in clays, CaCO₃ and nodules is represented by that for surface sediments, it has been possible to estimate an accumulation rate of phillipsite in pelagic sediments of the Pacific of 0.02 mg/cm²/yr.  相似文献   

Orthopyroxene-olivine assemblages in diogenites and mesosiderites     

Roger H. Hewins 《Geochimica et cosmochimica acta》1981,45(1):123-126

Diogenites contain equilibrated orthopyroxene-olivine assemblages. Mn is very regularly partitioned between olivine and orthopyroxene in pallasites, diogenites and synthetic eucrite melts, with an $\text{FeO}\text{MnO}$ partition ratio for olivine versus orthopyroxene of 1.6 by weight over a very wide range of FeO contents. In contrast to diogenites, Fe and Mn are not regularly partitioned between the olivine and orthopyroxene of mesosiderites and these minerals were not in equilibrium. Mesosiderite olivine differs from diogenite olivine in $\text{Fe}\text{Mn}$ and $\text{Ca}\text{Mn}$ ratios. Lack of olivine-orthopyroxene equilibrium suggests that olivine in mesosiderites was derived not from a pyroxenite component analogous to diogenites but from dunites.  相似文献   

The extent of oxygen isotope exchange between clay minerals and sea water     

Hsueh-Wen Yeh  Samuel M. Savin 《Geochimica et cosmochimica acta》1976,40(7):743-748

The extent of oxygen isotopic exchange between detrital clay minerals and sea water was investigated by analyzing $\text{O}{}^{18}\text{O}{}^{16}$ ratios of separated fine-grained size fractions of deep-sea sediments from three North Pacific ocean cores. Isotopic results were interpreted according to models based on the assumption that the extent of isotopic exchange should increase with decreasing particle size and increasing time of exchange between the sediment and sea water. The data indicate that information concerning the provenance and mode of formation of detrital clay minerals can be obtained from the $\text{O}{}^{18}\text{O}{}^{16}$ ratios of the coarser-than-0.1 μm fraction of deep-sea sediments younger than several million years and the finer-than-0.1 μm fraction of deep-sea sediments younger than several tens of thousands of years. Furthermore, if the extent of chemical reaction between detrital clays and sea water is similar to the extent of oxygen isotopic exchange, such reaction may be important in regulating the chemistry of sea water.  相似文献