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1.
Deep-sea nodules from the Northeast Pacific nodule belt and the Southeast Pacific (Sonne Basin), being formed in areas bordering the equatorial zone of high biological productivity, accumulate by two basically different growth processes: (A) early diagenetic growth by supply from pore water and (B) hydrogenetic growth by supply from near-bottom sea-water. These growth processes lead to different genetic types of nodules: early diagenetic type A, hydrogenetic type B, and mixed-type AB; a further type AC, very rich in Mn, is being formed by increasing influence of early diagenesis. These types can clearly be distinguished by their shapes, surface textures, mineral constituents of oxide fraction, internal microstructures, and geochemistry. A genetical classification is being proposed on the basis of statistically computed interelement relationships. Todorokite, very poor in Fe, is the main Mn phase in the early diagenetic substance; -MnO2 intimately intergrown with FeOOH · xH2O is the main phase in the hydrogenetic substance. Consequently an important difference can be pointed out: the metal supply for the growth of the early diagenetic nodules is based on an ionic solution of Me2+ (e. g. Mn2+, Ni2+, Cu2+, Zn2+), whereas the supply for the hydrogenetic nodules is caused by transport of colloidal particles. Mobilization of Mn2+ and fractionation from Fe is controlled by the amount of decomposing organic matter in the "peneliquid" layer of the sediments. The main factor controlling the intensity of early diagenesis is the biological productivity in surface waters. The crucial "point of reversal" at a Mn/Fe ratio of about 5, obtained by hyperbolical regression of the analyses of nodules from the Southeast Pacific, represents best concentrations in Ni and Cu. Mn/Fe quotients greater than 5 cause a decrease of Ni and Cu content. Nodules from the Northeast Pacific nodule belt generally contain higher concentrations in Cu than nodules from the Southeast Pacific. This can be explained by an additional supply of Cu transported below CCD by siliceous plankton.  相似文献   

2.
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   

3.
Marine sediments and ferromanganese nodules from the Pacific Ocean have been analyzed for the OMn ratio of solid manganese. We tested six chemical methods and concluded that the iodometric and oxalate methods were equivalent and were the best choice in terms of accuracy and precision on natural samples. We choose the iodometric method for most of our analyses because the oxalate procedure is a method of differences.The ferromanganese nodules that we analyzed were all from MANOP site H and had MnFe ratios that ranged from 5.6 to 70. These nodules were invariably highly oxidized with OMn values ranging from 1.90 to 2.00. Our most precise analyses suggest that less than 1% of the total manganese is present as Mn(II).We also analyzed red clay and hemipelagic sediments from the eastern tropical Pacific (Baja borderland and MANOP site H) and carbonate ooze samples from the equatorial Pacific. These sediments are also highly oxidized (OMn= 1.90 to 2.00) except when Mn(II) appears in the interstitial water. As dissolved Mn(II) increases the value of the OMn ratio in the solid phase decreases. The OMn ratio decreases to values as low as 1.40. This decrease appears to be due to a decrease in oxidized manganese by reduction, however, an increase in reduced manganese in the solid sediments by adsorption or MnCO3 formation can not be ruled out in all cases.  相似文献   

4.
Ferromanganese (Fe–Mn) crusts are strongly enriched relative to the Earth's lithosphere in many rare and critical metals, including Co, Te, Mo, Bi, Pt, W, Zr, Nb, Y, and rare-earth elements (REEs). Fe–Mn nodules are strongly enriched in Ni, Cu, Co, Mo, Zr, Li, Y, and REEs. Compared to Fe–Mn crusts, nodules are more enriched in Ni, Cu, and Li, with subequal amounts of Mo and crusts are more enriched in the other metals. The metal ions and complexes in seawater are sorbed onto the two major host phases, FeO(OH) with a positively charged surface and MnO2 with a negatively charged surface. Metals are also derived from diagenetically modified sediment pore fluids and incorporated into most nodules. Seafloor massive sulfides (SMS), especially those in arc and back-arc settings, can also be enriched in rare metals and metalloids, such as Cd, Ga, Ge, In, As, Sb, and Se. Metal grades for the elements of economic interest in SMS (Cu, Zn, Au, Ag) are much greater than those in land-based volcanogenic massive sulfides. However, their tonnage throughout the global ocean is poorly known and grade/tonnage comparisons with land-based deposits would be premature.The Clarion–Clipperton Fe–Mn Nodule Zone (CCZ) in the NE Pacific and the prime Fe–Mn crust zone (PCZ) in the central Pacific are the areas of greatest economic interest for nodules and crusts and grades and tonnages for those areas are moderately well known. We compare the grades and tonnages of nodules and crusts in those two areas with the global terrestrial reserves and resources. Nodules in the CCZ have more Tl (6000 times), Mn, Te, Ni, Co, and Y than the entire global terrestrial reserve base for those metals. The CCZ nodules also contain significant amounts of Cu, Mo, W, Li, Nb, and rare earth oxides (REO) compared to the global land-based reserves. Fe–Mn crusts in the PCZ have significantly more Tl (1700 times), Te (10 times more), Co, and Y than the entire terrestrial reserve base. Other metals of significance in the PCZ crusts relative to the total global land-based reserves are Bi, REO, Nb, and W. CCZ nodules and PCZ crusts are also compared with the two largest existing land-based REE mines, Bayan Obo in China and Mountain Pass in the USA. The land-based deposits are higher grade but lower tonnage deposits. Notably, both land-based deposits have < 1% heavy REEs (HREEs), whereas the CCZ has 26% HREEs and the PCZ, 18% HREEs; the HREEs have a much greater economic value. Radioactive Th concentrations are appreciably higher in the land-based deposits than in either type of marine deposit. A discussion of the differences between terrestrial and marine impacts and mine characteristics is also presented, including the potential for rare metals and REEs in marine deposits to be recovered as byproducts of mining the main metals of economic interest in nodules and crusts.  相似文献   

5.
Manganese at equilibrium in seawater occurs dominantly as Mn2+ and inorganic complexes at a concentration ratio of about 1:0.72; solubility decreases exponentially with increasing pH or Eh. However, the nodule oxides birnessite and todorokite are at least four orders of magnitude undersaturated relative to the Mn concentrations of seawater, and are metastable relative to hausmannite and manganite. This apparent lack of equilibrium is explicable by the mechanism of precipitation.Surfaces assist Mn precipitation by catalyzing equilibration between dissolved and reactive O2 and simultaneously also by adsorbing ionic Mn species. The effective Eh at the surface becomes 200–400 mV above that of seawater; the oxidation rate of Mn increases about 108 ×, and the activation energies for Mn oxidation decrease ~ 11.5 kcal/mole. Consequently, marine Mn nodules and crusts form by adsorption and catalytic oxidation of Mn2+ and ferrous ions at nucleating surfaces such as sea-floor silicates, oxyhydroxides, carbonates, phosphates and biogenic debris. The resulting ferromanganese surfaces autocatalyze further growth. In addition, Mn-fixing bacteria may also significantly accelerate accretion rates on these surfaces.Mn which accumulates in submarine sediments may be diagenetically recycled in response to steep solubility gradients causing upward migration from more acidic and reducing horizons toward the sea floor. In contrast, the concentrations of the predominant ferric complexes, Fe(OH)30 and Fe(OH)4?, are relatively less sensitive to the Eh's and pH's found in this environment; Fe is therefore not as readily recycled within buried sediments. Consequently, Fe is not so effectively enriched on the sea floor, although it precipitates more readily than Mn because seawater is saturated in amorphous Fe(OH)3.The metastable, perhaps kinetically-related, Mn oxides of nodules have a characteristic distribution: birnessite predominates in oxidizing environments of low sedimentation rate and todorokite where sedimentation rates and diagenetic Mn mobility are higher. Surface adsorption and cation substitution within the disordered birnessite-todorokite structure account for the high trace element content of Mn nodules.  相似文献   

6.

This study presents data on Fe–Mn nodules first recovered from the northeastern part of the Kara Sea. Analysis of the geochemical indicators of organic matter and major and trace element compositions of nodules showed that samples with strong Mn enrichment (Mn/Fe = 2.38, on average) are dominated by terrestrial organic matter (OM), whereas Fe-rich samples (Mn/Fe = 0.20, on average) are dominated by marine biogenic OM. The variation in the n-alkane abundances in the studied nodules is independent of the sampling sites and nodule morphology. This study was conducted for the first time in the Artic region.

  相似文献   

7.
The broad range of time over which ribbon bedded cherts were deposited does not extend into the present marine environment, and no ribbon cherts have been recovered from the sea floor by the Deep Sea Drilling Project. The depositional environment of bedded cherts is difficult to determine, but extra-silicic impurities in the rock may offer clues about the provenance of the non-biogenic component. To test the usefulness of relative abundances of the extra silicic components in extracting information on the depositional environment of the chert, I analyzed the major element chemistry of chert samples from a broad range of environments including ophiolite-associated chert from the Franciscan Formation of California, deep-sea chert and porcellanite from the northwest Pacific (DSDP Leg 32), shallow pelagic shelf chert nodules from the Chalk of Britain, continental marginal basin chert from the Monterey Formation of California, and continental marginal basin chert from the Pindos Zone of Greece. The ratios FeO/A12O3, TiO2/A12O3 and A1/A1+Fe+Mn were considered in detail. The interpretative logic is simple but empirically supported by observations of these ratio values at different depositional environments in the Pacific: A1 is concentrated most highly in continental material while Fe and Mn are more concentrated in pelagic sediments. FeO/A12O3 can be used to differentiate between ophiolite associated chert and chert associated only with other sediments. TiO2/A12O3 is not a useful indicator, possibly because of the equalizing effect of widespread eolian transport. The A1/A1+Fe+Mn ratio was measured in detail in one stratigraphic section in central continental Greece. This ratio varied with the type of sediment admixture, decreasing in value after the influx of ophiolite debris-bearing sediments, even when their presence was undetectable in hand sample or under petrographic microscope.To help clarify the paleogeography of the main study area, the Pindos Zone, and to identify sources and dispersal patterns of extra-basinal materials, isopach maps of sedimentary facies of the Pindos were constructed. Superimposed directly upon the series of imbricated thrust slices that comprise the Pindos Zone, the maps are at best compressed pictures of the Pindos Sea Floor. Persistent regional variation of facies thicknesses over time suggests the existence of several smaller depressions surrounded by submarine highs in the Pindos Basin.  相似文献   

8.
Results of the study of shallow-water ferromanganese nodules in the Gulf of Finland of the Baltic Sea, which are of practical interest for metallurgical and chemical industries, are discussed. The nodules contain the following elements: Mn, Fe, Si, Al, Na, Mg, Ti, K, V, Cu, Ni, Zn, P, and Ba. Contents of Mn (~30%) and Fe (~10%) are virtually similar to those in deep-sea oceanic nodules. However, concentrations of Ti, Cu, and Ni are notably lower than average values in oceanic nodules. The helium isotopic composition was studied to reveal cosmic dust in the nodule substance. The measured 3He and 4He concentrations are ~10?12 and ~10?5 cm3/g, respectively. The isotope ratio 3He/4He is approximately 10?7. More than 60% 3He is of cosmic (solar) origin, whereas 4He is of terrigenous (radiogenic) origin. Based on the cosmic duct concentration and the space tracer method, the FMN growth rate is estimated at 8–9 mm/ka at the nodule age varying from ~800 to 1500 yr. The growth rate of nodule has negative correlation with its size. Based on literature data, the growth rate of FMN from the western Baltic Sea is twice as high. An independent calculation of the FMN growth rate based on the diffusion-sorption mechanism (DSM) yielded 8.1 mm/ka, which is very close to the result based on the space tracer method. This value is proposed as the average growth rate of the studied nodules. Comparison with our previous measurements of growth rates for oceanic nodules showed that these values differ only slightly and are equal to n mm/ka, where n < 10. It is inferred that the formation mechanism of both marine and oceanic nodules is based on the same principles that control the generation of mobile forms of Mn in the bottom layer of sediments, i.e., principles related to bioproductivity of sea and ocean basins. Fluxes of lithogenic forms of Mn are of minor importance.  相似文献   

9.
《Applied Geochemistry》2004,19(6):973-979
The association of rare earth and other trace elements with Fe and Mn oxides was studied in Fe-Mn-nodules from a lateritic soil from Serra do Navio (Northern Brazil). Two improved methods of selective dissolution by hydroxylamine hydrochloride and acidified hydrogen peroxide along with a classical Na–citrate–bicarbonate–dithionite method were used. The two former reagents were used to dissolve Mn oxides without significant dissolution of Fe oxides, and the latter reagent was used to dissolve both Mn and Fe oxides. Soil nodules and matrix were separated by hand. Inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry after fusion with lithium metaborate, and X-ray diffraction were used to determine the elemental and mineralogical composition of the nodules and soil matrix. The latter was composed of kaolinite, gibbsite, goethite, hematite, and quartz. In the nodules, lithiophorite LiAl2(MnIV2MnIII)O6(OH)6 was detected in addition to the above-mentioned minerals. The presence of hollandite (BaMn8O16) and/or coronadite (PbMn8O16) in the nodules is also possible. In comparison to the matrix, the nodules were enriched in Mn, Fe, K, and P, and relatively poor in Si, Al, and Ti. The nodules were also enriched in all trace elements determined. Phosphorus, As and Cr were associated mainly with Fe oxides; Cu, Ni, and V were associated with both Fe and Mn oxides; and Ba, Co, and Pb were associated mainly with Mn oxides. Distribution of rare earth elements indicated a strong positive Ce-anomaly in the nodules, compared to the absence of any anomaly in the matrix. Some of Ce was associated with Mn oxides. The improved methods achieved almost complete release of Mn from the sample without decreasing the selectivity of dissolution, i.e., without dissolving significant amounts of Fe oxides and other minerals, and provided reliable information on associations of trace elements with Mn oxides. These methods are thus proposed to be included in sequential extraction schemes for fractionation of trace elements in soils and sediments.  相似文献   

10.
Rare earth elements in ferromanganese nodules and other marine phases   总被引:1,自引:0,他引:1  
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   

11.
Manganese oxides, which are widespread and of great practical importance, are formed and transformed by the active role of microorganisms. Manganese aggregates occur as both crystallized varieties and disordered fine-grained phases with significant ore grade and up to 50–60 vol % of X-ray amorphous components. X-ray amorphous nanosized Mn oxides in Fe-Mn nodules from the Pacific Ocean floor were examined from the standpoint of their biogenic origin. SEM examination showed abundant mineralized biofilms on the studied samples. The chemical composition of bacterial mass is as follows (wt %): 28.34 MnO, 17.14 Fe2O3, 7.11 SiO2, 2.41 CaO, 17.90 TiO2, 1.74 Na2O, 1.73 Al2O3, 1.30 MgO, 1.25 P2O5, 1.25 SO3, 0.68 CoO, 0.54 CuO, 0.53 NiO, and 0.50 K2O. The chemical composition of fossilized cyanobacterial mats within the interlayer space of nodulesis as follows (wt %): 48.35 MnO, 6.23 Fe2O3, 8.76 MgO, 5.05 Al2O3, 4.45 SiO2, 3.63 NiO, 2.30 Na2O, 2.19 CuO, 1.31 CaO, and 0.68 K2O is direct evidence for participation of bacteria in Mn oxide formation. This phase consists of mineralized glycocalix consisting of nanosized flakes of todorokite. Native metals (Cu, Fe, and Zn) as inclusions 10–20 μm in size were identified in ferromanganese nodules as well. The formation of nativemetals can be explained by their crystallization at highly reducing conditions maintained by organic matter.  相似文献   

12.
The occurrence of early diagenetic Ca‐rhodochrosite [(Mn,Ca)CO3] is reported in association with ‘griotte’‐type nodular limestones from basinal settings in the geological record; however, without the comparison of analogous modern examples, the controls on precipitation remain speculative. Here the findings of four layers of primary Ca‐rich rhodochrosite recovered from a modern deep‐sea setting in the Eastern Equatorial Pacific, from bioturbated sediments 300 m below sea floor, are reported (Ocean Drilling Program, Leg 201, Site 1226). The mineralogy is similar to cements in burrows recovered during Deep Sea Drilling Project Leg 68 at Eastern Equatorial Pacific Site 503 and from Ca‐rhodochrosite laminae in sediments of the central Baltic Sea. Petrographic relationships and constant oxygen isotopic compositions in the Ca‐rhodochrosite around 5‰ at all depths indicate a shallow burial depth of formation. The onset of 1‰ heavier oxygen isotope composition of Ca‐rhodochrosite at Site 503, about 30 m below the Pliocene/Pleistocene boundary, further suggests that precipitation occurs in the range of 30 m below sea floor. The approximate depth of formation allowed an approximate empirical fractionation factor for marine Ca‐rhodochrosite to be constrained that strongly differs from previously published theoretical values. Based on the approximate precipitation depth, authigenic Ca‐rhodochrosite forms within the SO42?‐reduction zone. Moderately negative δ13C values (around ?3‰) and total organic carbon lower than 2 wt% indicate a relatively low contribution of CO32? from organic C mineralization within the expanded redox zonation in the Eastern Equatorial Pacific. It is suggested that the alkalinity is increased by a rise in pH at focused sites of Mn‐reduction coupled with S2? oxidation. High concentrations of Mn‐oxide can accumulate in layers or burrows because of Mn‐cycling in suboxic sediments as suggested for the Baltic Sea Ca‐rhodochrosites. This study demonstrates how early diagenetic precipitates document biogeochemical processes from past diagenetic systems.  相似文献   

13.
14.
In iron-manganese nodules from the floor of Pacific ocean, Baltic, White Sea and Kara Sea, iron bydroxide '-FeOOH was analysed in the laboratory. In buried ooze, reduction processes generate Fe(HCO3)2 which migrates into the upper part of the bottom ooze and into near bottom sea water where Fe(OH)2 is formed. The oxidation process of Fe2+ to Fe3+, without participation of iron bacteria, leads to the topotactic transformation of Fe(OH)2 to '-FeOOH. Marine water does not contain Fe2+ and cannot be a direct source of iron deposited in the nodules. Discovery of '-FeOOH in marine nodules permits the consideration that both iron and manganese were derived from the buried bottom mud, which during diagenetic processes led to the transfer of these metals in solutions and their upward migration.  相似文献   

15.
The iron-bearing phases in nodules from two regions (the Pacific Ocean — Clarion-Clipperton, and the Indian Ocean — Central plain) have been studied by Mössbauer Spectroscopy. The major compounds are established to be Fe(OH)3, (FeOOH·H2O) and FeCO3. The value of the recoilless absorption probability f′ is measured for Fe(OH)3. Meisel's method for quantitative determination of iron containing compounds has been adapted for the case of nodule samples. By taking into account the f′ values, the error of quantitative determination is considerably reduced. The Fe2+ distribution in the nonequivalent M1 and M2 positions of pyroxene has been studied. It is shown that the pyroxene crystals in the silicate material originated as a result of rapid cooling of the magma in ocean water.  相似文献   

16.
Biogeochemical processes induced by the deposition of gravity layer in marine sediment were studied in a 295-day experiment. Combining voltammetric microelectrode measurements and conventional analytical techniques, the concentrations of C, O2, N-species, Mn and Fe have been determined in porewaters and sediments of experimental units. Dynamics of the major diagenetic species following the sudden sediment deposition of few cm-thick layer was explained by alternative diagenetic pathways whose relative importance in marine sediments is still a matter of debate. Time-series results indicated that the diffusion of O2 from overlying waters to sediments was efficient after the deposition event: anoxic conditions prevailed during the sedimentation. After a few days, a permanent oxic horizon was formed in the top few millimetres. At the same time, the oxidation of Mn2+ and then Fe2+, which diffused from anoxic sediments, contributed to the surficial enrichment of fresh Mn(III/IV)- and Fe(III)-oxides. Vertical diffusive fluxes and mass balance calculations indicated that a steady-state model described the dynamic of Mn despite the transitory nature of the system. This model was not adequate to describe Fe dynamics because of the multiple sources and phases of Fe2+. No significant transfer of Mn and Fe was observed between the underlying sediment and the new deposit: Mn- and Fe-oxides buried at the original interface acted as an oxidative barrier to reduced species that diffused from below. Nitrification processes led to the formation of a NO3/NO2 rich horizon at the new oxic horizon. Over the experiment period, NO3 concentrations were also measured in the anoxic sediment suggesting anaerobic nitrate production.  相似文献   

17.
Layers from one manganese nodule dredged from the Philippine Sea(16°56'N, 129°48'E; water depth, 5700 m) and 45 bulk nodules from offshore Minami-Torishima Island, Japan(23°3'N, 153°22'E; water depth, 1200 m) were analyzed chemically and their origin is discussed based on geochemical constraints. In general, Cu, Ni, Zn and Mo tend to increase with increasing Mn content, while Co, Pb, Ba, V, Sc, Th, and the rare earth elements(REEs) show less variation with increasing Mn content. Nodule 42 H from the Philippine Sea has an average Mn/Fe ratio close to 1 and shows a positive Ce anomaly, suggesting a predominant hydrogenous origin. Profiles of 230Th230 ex and Thex/232 Th ratios in the outer ~0.3 mm of nodule 42 H indicate a steady growth rate of ~1.7 mm/Myr. Nodule E30 from offshore Minami-Torishima is characterized by lower Mn, Fe, Mn/Fe(0.53) and Mo/V(0.2) ratios but higher P and Cu/Ni(0.31) ratio relative to other nodules from that area. The Ce content of E30 is unusually low(82 ppm) when compared with other nodules from the area and it is the only nodule analyzed with a negative Ce anomaly(-0.64). Based on the geochemical data we suggest that most nodules from offshore Minami-Torishima are primarily of hydrogenous origin except E30, which is dominated by hydrothermal input, and E45, which has about a 35% hydrothermal contribution.  相似文献   

18.
Two modifications of the delta-hydroxide of iron have been synthesized under laboratory conditions. Both are formed topotactically by the rapid course of the abiogenic reaction of the oxidation of Fe+2 at the expense of Fe(OH)2. Natural δ'-FeOOH, for which the authors propose the name "feroxyhyte," was found as yellowish-brown deposits in iron-manganese nodules from the bottom of the Pacific Ocean, Baltic, White, and Kara seas, and in gley soils. Feroxyhyte is an unstable hydrous oxide of iron, apparently transformed spontaneously into goethite, the stable modification of FeOOH. Its theoretical composition is Fe2O3 - 89.86, H2O - 10. 147%.  相似文献   

19.
Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn47.7 Ca45.1 Mg7.2) CO3. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.  相似文献   

20.
Summary ?Rocks containing braunite from the Ossa-Morena central belt (Iberian Massif, SW Spain) have been studied; these include nodules and layers of braunite (association I), Mn-slates (association II) and Mn-metatuffs (associations III and IV). Geochemical features of braunite nodules such as Mn/Fe ratios around 2, positive Ce-anomalies and good correlations among Mn, Fe, Co, Cu and REE contents indicate that the protolith of the braunite-nodules was precipitated from oxidising sea water. Greenschist facies Hercynian metamorphism reduced initial Mn4+ to Mn3+ and Mn2+. High initial fO2 of oxide beds (association I) limited reduction to the formation of braunite. Reduction continued until the formation of garnet + piemontite (associations II and III), and pyroxmangite + pyrophanite (association IV). Ti-rich braunites (up to 6.8% of TiO2) occur in slates and metatuffs in which the (Mn + Fe)/Ti ratio of the whole rock is lower than 30, while braunites have lower Ti contents in slates and metatuffs with (Mn + Fe)/Ti ratios around 90. Fe-rich braunite crystallized in rocks with Mn2+ oxide and silicate where low Mn3+/Mn2+ in the whole rock facilitated substitution of Fe3+ for Mn3+. Received January 30, 2002; revised version accepted May 7, 2002 Published online November 22, 2002  相似文献   

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