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1.
The Sr isotope stratigraphy of the biogenic apatite was used to determine the age of pelagic sediments in the Brazil Basin (Station 1541) that contain ferromanganese micronodules, nodules, and coatings on the weathered volcanic rocks. The age of sediments at horizons 0–5 and 86–90 cm was estimated at 24.1 ± 0.2 Ma and 24.8 ± 0.2 Ma, respectively. The average sedimentation rate in the Late Oligocene was about 13 mm/ka. The hydrogenous Fe–Mn nodule on the sediment surface with the Mn/Fe value of 1.05–1.95 was formed at a rate of 1.2–2.4 mm/Ma, which is 1000 times lower than the growth rate of buried nodule (Mn/Fe 0.4) at depth of 83 cm. Diagenesis provoked changes in the mineral composition of the buried nodule (asbolane-buserite partially replaced by goethite), leading to the loss of a part of Mn, Ni, Li, and Tl but accumulation of trace elements linked with iron oxyhydroxides (Ce, Th, Be, As, and V) were retained. The composition of manganese micronodules at two studied depths in sediments evolved in the course of two stages of ore formation: related to the oxic and suboxic diagenesis. The Sr isotopic composition in manganese micronodules from both horizons do not differ from that of dissolved Sr in the ocean water. The 143Nd/144Nd ratio, which reflects the Nd isotopic composition in the paleocean during the micronodule formation, varies in manganese micronodules from different horizons and is constant in different size fractions.  相似文献   

2.
Measurements of 238U, 234U, 230Th, 232Th, 231Pa, Mn, Fe, Co, Ni, Cu, and Zn were made on 23 samples from core GPC-5, a 29-m giant piston core from a water depth of 4583 m on the northeastern Bermuda Rise (33°41.2′N, 57°36.9′W). This area is characterized by rapid deposition of sediment transported by abyssal currents. Unsupported 230Th and 231Pa are present throughout the core but, because of large variations in the sedimentation rate, show marked departures from exponential decay with depth. The trend with depth of the 231Paex230Thex ratio is consistent with the average accumulation rate of 36 cm/1000 y reported earlier on the basis of radiocarbon dating and CaCO3 stratigraphy. When expressed on a carbonate-free basis, concentrations of Mn, Co, Ni, Cu, Zn, 230Thex, and 231Paex all show cyclic variations positively correlated with those of CaCO3. The correlations can be explained by a model in which all of these constituents, including CaCO3, are supplied to the sediments from the water column at a constant rate. Concentration variations are controlled mainly by varying inputs of terrigenous detritus, with low inputs occurring during interglacials and high inputs during glacials. Relationships between the metal and 230Thex concentrations permit estimates of the rates at which the metals are removed to the sediment by scavenging from the water column. The results, in μg/cm2-1000 y, are: 4300 ± 1100 for Mn, 46 ± 16 for Ni and 76 ± 26 for Cu. These rates are somewhat larger than ocean-wide averages estimated by other methods, and the absolute rate of 230Th accumulation in GPC-5 averages about nine times higher than production in the overlying water column. This part of the Bermuda Rise and similar bottom-current deposits may act as important accumulators of elements scavenged from seawater.  相似文献   

3.
Thorium- and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4 mm to gain a high-resolution230Thexcess profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We got values of 0.06–0.59 ppb (230Th), 0.43–1.40 ppm (232Th), 0.09–0.49 ppb (234U) and 1.66–8.24 ppm (238U). The uranium activity ratio in the uppermost samples (1–6 mm) and in two further sections in the nodule at 12.5±1.0 mm and 27.3–33.5 mm comes close to the present ocean water value of 1.144±0.004. In two other sections of the nodule, this ratio is significantly higher, probably reflecting incorporation of diagenetic uranium. The upper 25 mm section of the Mn nodule shows a relatively smooth exponential decrease in the230Thexcess concentration (TIMS). The slope of the best fit yields a growth rate of 110 mm/Ma up to 24.5 mm depth. The section from 25 to 30.3 mm depth shows constant230Thexcess concentrations probably due to growth rates even faster than those in the top section of the nodule. From 33 to 50 mm depth, the growth rate is approximately 60 mm/Ma. Two layers in the nodule with distinct laminations (11–15 and 28–33 mm depth) probably formed during the transition from isotopic stage 8 to 7 and in stage 5e, respectively. The Mn/Fe ratio shows higher values during interglacials 5 and 7, and lower ones during glacials 4 and 6. A comparison of our data with data from adjacent sediment cores suggests (a) a variable supply of hydrothermal Mn to sediments and Mn nodules of the Peru basin or (b) suboxic conditions at the water sediment interface during periods with lower Mn/Fe ratios.  相似文献   

4.
Hydrogenetic ferromanganese crusts (Fe-Mn crusts) provide a secular record of the variations of seawater composition responding to changes in ocean circulation and erosion processes. In this respect, the acquisition of an absolute and reliable chronology in Fe-Mn crusts is a prerequisite. Here we combine four different and complementary chronometers (10Be, 230Thex, 230Thex/232Th, 234U/238U) in a Fe-Mn crust dredged at ∼2000 m depth in the east Atlantic to first establish a reliable chronology over the Quaternary period. Then, we use EDS chemical analysis to look for correlation between major element chemistry and climate changes. (230Thex), (230Thex/232Th), and Be data give very consistent growth rates. In particular, the good match between (230Thex) and (230Thex/232Th) data indicates that at the location of crust 121DK, 230Th and 232Th fluxes in the water column change simultaneously and suggests that the normalization of 230Thex to 232Th makes (230Thex/232Th) a better chronometer. Our best-fit model suggests that crust 121DK experienced changes in growth rates at ∼122 and 312 ka and a growth with a constant 230Th initial flux. This chronology returns an age of 680 ka for the uppermost 1.5 mm. The (234U/238U) depth profile, however, was clearly affected by diffusion of 234U in the porous crust and can therefore not be used to derive a reliable chronology. One part of the crust seems isolated from pore water diffusion and can be physically recognized as a zone of very small porosity. On the basis of the (230Thex/232Th) chronology, major element chemistry is shown to be linked to climate change. Mn/Fe variations compare well with those in a Fe-Mn crust from the Pacific, showing systematic maxima during glacial stages 2 and 4. High Mn/Fe are tentatively interpreted to reflect expansion of the oxygen minimum zone during glacial periods, resulting from higher bioproductivity. In addition we note that the surface (230Th/232Th) activity ratio of crust 121DK is entirely consistent with advection of deep water from the western toward the eastern Atlantic basin.  相似文献   

5.
Estimates of the growth rates of ferromanganese nodules at MANOP Site H (6°33′N, 92°49′W) lie between 7 and 1200 mm/my. The most probable range (estimated from nodule size distributions, nodule chemistry, accumulation rates of authigenic elements and U-series modeling) is 30–300 mm/my. Such rates are much faster than measured values for most pelagic nodules. The distributions of U-series and stable elements suggest that a typical nodule consists of two compositionally distinct non-detrital components, one rich in Mn, U and Sb, and the other in Fe, Co, REE, Ni, Cu and Th. When the uncorrected U-series data, which do not show simple decay patterns with depth, are normalized to the relative proportion of the Fe-rich component, the data yield well-constrained growth rates of 55 mm/my for a nodule top and 200 mm/my for its bottom. The component enriched in Mn, which is most abundant on nodule bottoms, appears to accrete much faster than the component enriched in Fe.  相似文献   

6.
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7.
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   

8.
Rare earth element (REE) distributions and 87Sr/86Sr ratios were determined for nodule crusts and associated surface sediments collected in the southeastern Pacific Ocean between South America and the Tuamotu archipelago. The shale-normalized patterns of the REE from the surface sediments show pronounced negative anomalies in Ce which indicate a marine origin. One 87Sr/86Sr ratio also has a value characteristic for seawater strontium. REE patterns from the nodule crusts, when normalized to shales, seawater or associated surface sediment, show that a marine origin can also be proposed for the oxy-hydroxides. Only the Ce shows a systematic scatter, which could be the result of fluctuations in the oxidation-reduction conditions during nodule growth. The marine origin for REE is corroborated by the 87Sr/86Sr ratios which average 0 · 70905 ± 0 · 00019 (2σ), a value close to the seawater 87Sr/86Sr ratio of 0·70910 ± 0 · 00035. If the major metals of the polymetallic nodules have the same origin as these trace elements, then a direct precipitation from seawater can be postulated for the crusts studied here.  相似文献   

9.
Whale carcasses (whale falls) deposited on the deep seafloor are associated with a distinctive biotic community. A fossil whale bone recovered from São Paulo Ridge, South Atlantic Ocean, during cruise YK13–04 Leg 1 of R/V Yokosuka was covered by a ferromanganese (Fe–Mn) crust approximately 9 mm thick. Here, we report an age constraint for this fossil bone on the basis of Os isotopic stratigraphy (187Os/188Os ratio) of the Fe–Mn crust. Major‐ and trace‐element compositions of the crust are similar to those of Fe–Mn crusts of predominantly hydrogenous origin. Rare earth element concentrations in samples of the crust, normalized with respect to Post‐Archean average Australian Shale, exhibit flat patterns with positive Ce and negative Y anomalies. These results indicate that the Fe–Mn crust consists predominantly of hydrogenous components and that it preserves the Os isotope composition of seawater at the time of its deposition. 187Os/188Os ratios of three Fe–Mn crust samples increased from 0.904 to 1.068 in ascending stratigraphic order. The value of 1.068 from the surface slice (0–3 mm depth in the crust) was identical to that of present‐day seawater within error (~1.06). The value of 0.904 from the basal slice (6–9 mm) equaled seawater values from ca. 4–5 Ma. Because it is unknown how long the bone lay on the seafloor before the Fe–Mn crust was deposited, the Os stratigraphic age of ca. 5 Ma is a minimum age of the fossil. This is the first application, to our knowledge, of marine Os isotope stratigraphy for determining the age of a fossil whale bone. Such data may offer valuable insights into the evolution of the whale‐fall biotic community.  相似文献   

10.
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 230Th232Th, 227Th230Th, and 10Be9Be. 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   

11.
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   

12.
The major and minor element composition of ferromanganese nodules from DOMES Site A has been determined by X-ray fluorescence methods. Three phases appear to control the bulk compositions: Mn and Fe oxyhydroxides and aluminosilicates. Relatively wide compositional variations are evident throughout the area. Nodules with high Mn/Fe ratios, high Cu, Mg, Mo, Ni and Zn concentrations and high todorokite/δ-MnO2 ratios have granular surface textures and are confined to an east-west trending depression with thin Quaternary sediment cover. Nodules with low Mn/Fe ratios, high concentrations of As, Ca, Ce, Co, La, P, Sr, Ti, V, Y and Zr and low todorokite/δ-MnO2 ratios have smooth surfaces and are confined to shallower areas with relatively thick Quaternary sediment to the north and south of the depression.All nodules in the area have compositions which are influenced by diagenesis, but those with the most marked diagenetic signature (high Mn/Fe and Cu/Ni ratios, low Ce/La ratios and more todorokite) are found in areas of very slow or non-existent sedimentation; many of these nodules are actually in contact with outcropping Tertiary sediment. This paradox may be resolved by postulating, by analogy with some shallow-water occurrences, that the nodules accrete from bottom waters which have enhanced particulate and dissolved metal contents derived from diagenetic reaction in areas remote from the site of nodule formation. The metals are supplied in a bottom flow (probably Antarctic Bottom Water) which also erodes, or prevents modern sedimentation in, the depression. Nodules on the flanks of the depression are not evidently affected by this flow and derive at least pan of their constituent metals from diagenetic reaction in the underlying Quaternary sediment.Apparently, abyssal diagenetic nodules can have an immediate and a remote diagenetic metal source. Metal fluxes derived from pore water dissolved metal gradients may not be relevant to particular accreting nodules if a significant fraction of their metals is derived from outside the area in which they form.  相似文献   

13.
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   

14.
Processes of authigenic manganese ore formation in sediments of the northern equatorial Pacific are considered on the basis of study of the surface layer (<2 mm) of ferromanganese nodule and four micronodule size fractions from the associated surface sediment (0–7 cm). Inhomogeneity of the nodule composition is shown. The Mn/Fe ratio is maximal in samples taken from the lateral sectors of nodule at the water-sediment interface. Compositional differences of nodules are related to the preferential accumulation of microelements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenous component trapped during nodule growth (Ga, Rb, Ba, and Cs). The Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by the minimal Mn/Fe values. The compositional comparison of manganese micronodules and surface layers of the nodule demonstrated that the micronodule material was subjected to a more intense reworking during the diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe ratios but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are least mobile elements during the diagenesis of elements. Differences in the chemical composition of micronodules and nodules are related not only to the additional input of Mn in the process of diagenesis, but also to the transformation of iron oxyhydroxides after the removal of Mn from the close association with Fe formed in the suspended matter at the stage of sedimentation.  相似文献   

15.
Fourteen ferromanganese nodule–sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule–sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo – (307, 273), Ni – (71, 125), Mn – (64, 87), Cu – (43, 80), Co – (23, 75), Pb – (15, 24), Zn – (9, 11) and V – (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation (r ? 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.  相似文献   

16.
Rare earth element zonation in Pacific ferromanganese nodules   总被引：1，自引：0，他引：1  
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 MnFe 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   

17.
《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   

18.
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   

19.
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   

20.

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.

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