Geochemical and mineralogical control of different genetic types of deep-sea nodules from the Pacific Ocean

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 A_C, 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.     

Composition of manganese nodules and manganese carbonates from Loch Fyne,Scotland

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 (Mn_47.7 Ca_45.1 Mg_7.2) 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.     

Thorium and uranium isotopes in a manganese nodule from the Peru basin determined by alpha spectrometry and thermal ionization mass spectrometry (TIMS): Are manganese supply and growth related to climate?

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-resolution²³⁰Th_excess 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 the²³⁰Th_excess 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 constant²³⁰Th_excess 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.     

Geochemistry and specific features of manganese ore formation in sediments of oceanic bioproductive zones

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.     

The distribution of U and Th in growth zones of manganese nodules

Growth zones and individual sublayers from one manganese nodule and three manganese crusts from an area south of Hawaii were analysed for U and Th by the delayed-neutron counting technique.The concentrations of uranium and thorium in the manganese nodule are highest in the outermost zone on top of the nodule, being the surface last exposed to sea water. In this zone U varies from 6.3 to a maximum of 8.3 ppm in different sublayers, decreasing to 5.0 ppm in the inner zones and 3.4 ppm in the outer zone last exposed to the sediment. Ferromanganese material scraped from the zone last exposed to the sediment which has low concentrations of Fe, relative to the zone last exposed to sea water, has also low U contents (2.7 ppm).Th concentrations are higher in the outermost zone on top of the nodule (40 to a maximum of 130 ppm) than in the zone last exposed to the sediment (about 20 ppm Th).Manganese crusts contain up to 9 ppm U in the outermost zones last exposed to the sea water. They also have higher concentrations of Th (up to 64 ppm) relative to the inner zones of the crust growing on altered andesitic rock, which contains about 8 ppm U and about 26 ppm Th as an average.     

Geochemistry and Origin of Layers in Single Manganese Nodule from the Philippine Sea and Manganese Nodules from Offshore Minami-Torishima,Western Pacific

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.     

Rare elements and Nd and Sr isotopic composition in micronodules from the Brazil Basin,Atlantic Ocean

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.     

Geochemistry of ferromanganese nodule–sediment pairs from Central Indian Ocean Basin

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.     

Composition and formation of fossil manganese nodules in Jurassic to Cretaceous radiolarites from the Nicoya Ophiolite Complex (NW Costa Rica)

Horizons of several types of Upper Jurassic to Lower Cretaceous manganese nodules occur locally in sequences of radiolarian cherts within the Nicoya Ophiolite Complex (NW Costa Rica). Field studies, X-ray diffraction analysis, petrographic, chemical and experimental studies give evidence of a sedimentary, early diagenetic origin of the nodules, in contrast to earlier suggestions. Smooth, discoidal, compact and very dense nodules with diameters of some mm to 9 cm dominate. They are characterized by braunite, hollandite, pyrolusite and quartz as well as 39–61% Mn, 0.9–1.6% Fe, 5–26% SiO₂, 1.3–1.9% A1₂O₃, 1.5–3.0% Ba, 460–5400 ppm Cu, 85–340 ppm Ni and 40–130 ppm Co, among others. It is suggested that the original mineralogy (todorokite?) was altered during thermometamorphic (braunite) and hydrothermal (hollandite, pyrolusite) events. Petrographic similarities between the fossil nodules and modern deep-sea nodules are striking. Using standard hydrothermal techniques in an experimental study it is shown that under special conditions, braunite can be produced from modern nodule material.     

Critical metals in manganese nodules from the Cook Islands EEZ,abundances and distributions

The Cook Islands (CIs) Exclusive Economic Zone (EEZ) encompasses 1,977,000 km² and includes the Penrhyn and Samoa basins abyssal plains where manganese nodules flourish due to the availability of prolific nucleus material, slow sedimentation rates, and strong bottom currents. A group of CIs nodules was analyzed for mineralogical and chemical composition, which include many critical metals not before analyzed for CIs nodules. These nodules have varying sizes and nuclei material; however all are composed predominantly of δ-MnO₂ and X-ray amorphous iron oxyhydroxide. The mineralogy, Fe/Mn ratios, rare earth element contents, and slow growth rates (mean 1.9 mm/10⁶ years) reflect formation primarily by hydrogenetic precipitation. The paucity of diagenetic input can be explained by low primary productivity at the surface and resultant low organic matter content in seafloor sediment, producing oxic seafloor and sub-seafloor environments. The nodules contain high mean contents of Co (0.41%), Ni (0.38%), Ti (1.20%), and total rare earth elements plus yttrium (REY; 0.167%), and also high contents of Mo, Nb, V, W, and Zr.Compiled data from a series of four cruises by the Japan International Cooperation Agency and the Mining agency of Japan from 1985 to 2000 were used to generate a map that defines the statistical distribution of nodule abundance throughout the EEZ, except the Manihiki Plateau. The abundance distribution map shows a belt of high nodule abundance (19–45 kg/m²) that starts in the southeast corner of the EEZ, runs northwest, and also bifurcates into a SW trending branch. Small, isolated areas contain abundances of nodules of up to 58 kg/m². Six ~ 20,000 km² areas of particularly high abundance were chosen to represent potential exploration areas, and maps for metal concentration were generated to visualize metal distribution and to extrapolate estimated metal tonnages within the six sites and the EEZ as a whole. Grades for Mn, Cu, and Ni are low in CIs nodules in areas of high abundance; however, Ti, Co, and REY show high contents where nodule abundances are high. Of the six areas identified to represent a range of metal contents, one at the northern end of the N-S abundance main belt optimizes the most metals and would yield the highest dry metric tons for Mn (61,002,292), Ni (1,247,834), Mo (186,166), V (356,247), W (30,215), and Zr (195,323). When compared with the Clarion–Clipperton Zone, the CIs nodules show higher nodule abundances (> 25 kg/m² over ~ 123,844 km²), and are more enriched in the green-tech, high-tech, and energy metals Co, Ti, Te, Nb, REY, Pt, and Zr. The CIs EEZ shows a significant resource potential for these critical metals due to their high prices, high demand, and the high nodule abundance, which will allow for a smaller footprint for a 20-year mine site and therefore smaller environmental impact.     

Suboxic trace metal geochemistry in the Eastern Tropical North Pacific

We analyzed Al, Ti, Fe, Mn, Cu, Ba, Cd, U, Mo, V, and Re in water column, settling particulate, and sediment (0 to 22 cm) samples from the intense oxygen minimum zone (OMZ) of the eastern tropical North Pacific near Mazatlán, Mexico. The goal was to determine how the geochemistry of these elements was influenced by suboxic water column conditions and whether the sediments have a unique “suboxic” geochemical signature.The water column was characterized by a Mn maximum, reaching ∼8 nmol kg⁻¹ at 400 m. Concentrations of Cu, Ba, Cd, Mo, Re, U, and V were unaffected by the low O₂ conditions and were comparable to those of the open ocean. Sinking particles were composed of lithogenic particles of detrital origin and nonlithogenic particles of biogenic origin. Al, Ti, and Fe were mostly (at least 79%) lithogenic. About 75% of the Mn was nonlithogenic. Significant amounts (at least 58%) of Cu, Ba, Cd, and Mo were nonlithogenic.Sediment geochemistry varied across the continental shelf and slope. Cadmium, U, and Re have prominent maxima centered at 310 m, with 12.3 ppm, 10.9 ppm, and 68.3 ppb, respectively, at the core top. High values of Mo (averaging 6.8 ppm) and V (averaging 90 ppm) are seen in OMZ surface sediment. Additional down-core enrichment occurs for all redox-sensitive elements in the top 10 cm. For U, Mo, V, and Re, surface sediments are a poor indicator of metal enrichment. Comparison of the nonlithogenic composition of sediments with sinking particles suggests that direct input of plankton material enriched in metals makes a significant contribution to the total composition, especially for Cd, U, and Mo.We evaluated Re/Mo and Cd/U ratios as tracers for redox environments. Rhenium and Mo concentrations and Re/Mo ratios do not lead to consistent conclusions. Concurrent enrichments of Re and Mo are an indicator of an anoxic depositional environment. In contrast, high Re/Mo ratios are an indicator of suboxic conditions. Cadmium is enriched in surface sediments, while U has considerable down-core enrichment. The concentrations of Cd and U and the Cd/U ratio do not follow patterns predicted from thermodynamics. Though the water column is suboxic, these four redox-sensitive elements indicate that the sediments are anoxic. The implication for paleostudies is that a trace metal sediment signature that indicates anoxic conditions is not necessarily attributable to an anoxic water column.     

Estimating growth rates of ferromanganese nodules from chemical compositions: implications for nodule formation processes

Using available information on the accretion rates and the bulk chemical compositions of oceanic ferromanganese nodules, it can be shown that the accumulation rate of manganese is proportional to the square of the accumulation rate of iron. This relationship has been used to derive an equation that predicts nodule growth rates from their chemical compositions. The equation accurately predicts growth rates up to about 50 mm/10⁶ yr, but yields incorrect rates for faster-growing concretions. From this relationship nodules underneath water of high primary productivity grow most rapidly and accumulate transition metals most rapidly; however, nodules from regions of highest primary productivity do not have the highest concentrations of nickel and copper. Reduction of manganese within the sediment column and remobilization of a fraction to the surface sediments adds manganese to nodules without substantially augmenting the supply of other transition elements. The addition of remobilized manganese to the nodule dilutes the concentrations of nickel, copper and iron, even though their rates of accumulation are also high.     

太平洋中国开辟区锰结核生物成因研究

本文对叠层石（微小叠层石与奇异叠层石）及其建造者（中华微放线菌与太平洋螺球孢菌）在结核中显示的规律性特征,叠层石纹层与超微生物生长,主要锰矿物及Fe、Mn元素与叠层石类型之间关系以及超微生物直接成矿等作了深入研究。结果表明：锰结核中叠层石柱体一般都显示出纹层、纹层组与纹层带3个级别的生长韵律,明层菌丝体密集,暗层菌丝体稀疏;两种叠层石类型与超微生物化石种存在着良好的对应关系;主要锰矿物含量变化与叠层石类型密切相关;叠层石柱体内Fe、Mn元素分布比柱间空隙具有明显的规律性,而全球性大气化程度比生殖菌丝强;超微生物的生化作用与沉积粘附作用直接造成了结核中Fe、Mn元素的富集,而全球性大气修与洋底微环境的周期性变化,影响了微生物生长的兴衰,导致了明暗相间纹层的交替出现。我们认为,叠层石纹层显示的韵律性特征,是胶体化学作用与沉积作用难以形成的,只有微生物群体的世代繁衍,才能构筑成几乎固定不变的叠层石柱体形态。上述研究成果,进一步确立了大洋锰结核的生物成因观点。     

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

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.     

Rare earth elements in ferromanganese nodules and other marine phases

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.     

Mineralogical criteria in the origin of marine iron-manganese nodules

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.     

The development of Fe-nodules surrounding biological material mediated by microorganisms

Takashikozo is a phenomenon of Quaternary sediments in Japan. They are cylindrical Fe-oxyhydroxide nodules that form as plaques round plant roots, where Fe is preferentially concentrated to develop a solid wall. Structural features suggest that after the roots have decayed, the central space where the roots were situated acts as a flow path for oxidized water. Analysis of microbial 16S rDNA extracted from the nodules identified iron-oxidizing bacteria encrusted round the roots where they are the likely initiators of nodule formation. Direct microscopic observation revealed an accumulation of Fe-oxyhydroxides that fill the pore spaces and is also likely to be linked with the encrusting microbial colonies. Geological history and nanofossil evidence suggest that these Fe-nodules may have been buried at a depth of up to several tens of meters for at least 10⁵ years in reducing Quaternary sediments. Thus Fe-oxyhydroxide nodules that have formed in a geological environment at the interfaces between water and rock by microbial mediation can persist under reducing conditions. If this is the case, the phenomenon is significant as an analogue of post-closure conditions in radioactive waste repositories, since it could influence nuclide migration.     

Geochemistry of uranium in sediments of the Bohai Gulf,China

The following conclusions can be drawn from the work reported in this paper:

1. Sixteen samples were determined for uranium by spectrophotometric method. The uranium content in the sea floor sediments of the Bohai Gulf ranges from 1.6 to 6.3 ppm, with an average of 4.3 ppm.
2. Statistical data show close relationship between U concentration and grain size. Relatively larger amount of uranium was found accumulated in mud than in sand. The bulk of uranium is assumed to be derived from terrestrial detrital minerals.
3. A positive correlation between U and Fe is recognized. Similar relation also can be seen between U and Al. The plot of U concentration vs. Fe is linear, and can be expressed by the linear regression equation:Y=?0.37+1.35X. The plot of U against Al gives an equation ofY=?2.48+1.01X.
4. The average U/C_org. ratio for these sediments is 7×10^?4, and the average ratios of U/P, U/Mn, and U/CaCO₃ are 100×10^?4, 50×10^?4 and 2×10^?4, respectively.
5. Compared with the abundances of other shelf sediments, the average concentration of U in the area under consideration is close to that of sediments on the selves of Japan and the Gulf of Mexico, and the Black Sea. Uranium concentration in the Bohai Gulf sediments is comparable to that of the continental crust, but differs from that of deep-sea clay.

     

The oxidation state of manganese in marine sediments and ferromanganese nodules

Marine sediments and ferromanganese nodules from the Pacific Ocean have been analyzed for the $\text{O}\text{Mn}$ 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 $\text{Mn}\text{Fe}$ ratios that ranged from 5.6 to 70. These nodules were invariably highly oxidized with $\text{O}\text{Mn}$ 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 ($\text{O}\text{Mn}\text{= 1.90 to 2.00}$) except when Mn(II) appears in the interstitial water. As dissolved Mn(II) increases the value of the $\text{O}\text{Mn}$ ratio in the solid phase decreases. The $\text{O}\text{Mn}$ 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.     

Detailed geochemical studies of a He-U lake anomaly in permafrost, Baker Lake Area, N.W.T.

A strong He-U anomaly, discovered in the Thelon basin of the N.W.T. during a regional U exploration program in 1981, was studied in detail in 1982. The anomaly is confined to a 3-km² lake situated 160 km northwest of Baker Lake. Lake bottom water and sediment samples taken in June through the ice on a 50 m × 50 m grid, were analyzed for a number of trace and minor elements.In the lake sediments He and U were highly anomalous and parallel the strong anomaly patterns of He observed in the water. Median and maximum values in the sediments were 57 ppm and 396 ppm U, and 296 nL/L and 13870 nL/L He. Regional medians were 4.3 ppm U and 50 nL/L He. Se and V in sediments gave weak but similar anomaly patterns to those observed for U and He.The anomaly is somewhat of an enigma. The unusually high U content indicates an oxidizing, hence, near surface, water regime, and the highly anomalous He flux into the lake and a thick cover of permafrost in the region indicate a very deep source where conditions are normally reducing, rendering U immobile.Coincident anomaly patterns and increasing concentrations with depth of minor and trace elements and gases in the lake water prove that groundwater is the source of the anomalies. Contoured element maps indicate that this groundwater enters the lake in at least four places.The fact that up to 35 ppb U, 6 ppm dissolved O₂ and virtually no Fe and Mn, were detected in lake waters above groundwater entry points indicates that the groundwaters were oxidizing with respect to these elements. This is indeed surprising because permafrost is believed to be about 300 m thick in the region; at such depths groundwaters are usually rich in Fe and void of U.The highly anomalous He in this lake indicates deep fractures which serve as conduits for mineralized water entering the lake from depth and creating a frost-free window in the permafrost. The fractures probably penetrate well into the basement for only major deep fractures are known to produce such strong He anomalies. The additional presence of anomalous U suggests U mineralization at depth.