锰结核生长与沉积环境的关系

本文收集了48组世界大洋各种沉积环境锰结核化学组成和生长速率数据并计算了它们的铁锰通量；讨论了不同环境的锰结核的铁锰含量之间的关系，以及锰通量与铁通量、Mn/Fe比的相关性；导出了由锰结核锰铁含量计算生长速率的经验关系；从本质上揭示了锰结核化学组成、生长速率与沉积环境的内在联系，为探讨锰结核形成机理提供了有力的依据。     

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.     

大洋锰结核中钴的赋存状态及提取实验研究

为合理有效地提取和利用大洋金属资源,在对大洋锰结核化学成分及矿物组成进行测定的基础上,采用分布溶解法对钴的赋存状态进行了分析.选择还原氨浸法对大洋锰结核中的多金属进行了浸取实验,并用铵黄铁矾法对浸取液进行了除铁及用硫化沉淀法对钴进行分离提取等实验.结果表明:大洋锰结核中钴的质量分数可达0.30%,且主要以硅酸钴、氧化钴和硫化钴的形式存在.氨浸提取可以有效地使金属离子从结核中溶出,其中钴的浸出率最高可达93.25%;铵黄铁矾法可将浸出液中的铁全部去除.提取的硫化钴中除含有少量铬外未见其它杂质元素.     

A geochemical comparison of manganese oxide deposits of the Hawaiian Archipelago and the Deep Sea

Data are presented on the composition of manganese crusts collected within the Hawaiian Exclusive Economic Zone (HEEZ). These crusts were obtained in 80% of the dredge hauls between 800 and 3000 m. Although the chemistries of crusts on the Cenozoic Hawaiian Ridge and an older Cretaceous seamounts south and north of the ridge are quite similar, there are marked differences, both in composition and in mineralogical organization, between shallow and deep crusts. Shallow crusts (<1500 m) are composed of five distinct phases (i.e. silicate, apatite, iron oxide, manganese oxide, and non-associated copper), whereas the deep crusts display no obvious inter-elemental organization based on dendrograms. The mean composition of HEEZ crusts differs from that of Eastern Tropical Pacific nodules in that crusts are comparatively rich in As, Pb, Co, Ce, Fe, and Ti, whereas nodules have comparatively more Cu, Ni, and Sr. Compositional differences between shallow crusts and nodules are discussed in terms of (1) element source; (2) Mn-oxide mineralogy; and (3) redox conditions in the adjacent seawater. It is concluded that the major differences between crust and nodules is due to metal sources; water column for crusts, sediments for nodules. Advective processes within the O₂ minimum also affect the HEEZ crusts.     

The aluminosilicate fraction of North Pacific manganese nodules

Nine nodules collected from throughout the deep North Pacific were analyzed for their mineralogy and major-element composition before and after leaching with Chester-Hughes solution. Data indicate that the mineral phillipsite accounts for the major part (> 75%) of the aluminosilicate fraction of all nodules. It is suggested that formation of phillipsite takes place on growing nodule surfaces coupled with the oxidation of absorbed manganous ion. All the nodules could be described as ternary mixtures of amorphous iron fraction (Fe-Ti-P), manganese oxide fraction (Mn-Mg Cu-Ni), and phillipsite fraction (Al-Si-K-Na), these fractions accounting for 96% of the variability of the chemical composition.     

The composition of ferromanganese nodules of the Chukchi and East Siberian seas

Ferromanganese nodules from the floors of the Chukchi and East Siberian seas were examined by means of analytical electron microscopy and plasmic and chemical analysis. It was found that the nodules consisted of aggregates of colloform and poorly crystallized matter of globular and irregular shapes, in which the minerals of iron and manganese were mainly presented by hematite, vernadite, and asbolane. The samples from the Chukchi Sea contained single micrograins of native gold. The tested nodules were comparable to oceanic ones in iron content. The contents of manganese, ore elements, and most of microelements are well below those of the ocean. The comparison of the composition of bottom sediments and considered nodules showed that the latter were enriched during their formation by factors of 100–200 in manganese, of 10–18 in cobalt, and of 4–8 in iron, nickel, and zinc. However, the process of diagenetic accumulation of metals by nodules in the marine environment is less effective than in the open ocean with the sediments of higher con-tent of mobile element forms and of higher exposure time compared to marine sediments.     

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.     

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 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.     

Sandstone-hosted thorium-bitumen mineralization in the Northwest Irish Basin

Low-grade sandstone-hosted thorium mineralization is recorded in the Carboniferous Northwest Irish Basin in the Republic of Ireland and Northern Ireland. The thorium is concentrated within bitumen nodules which are replacive within the sandstones. A source of thorium was available in a Caledonian granite in the basin watershed, and the bitumen was a product of hydrocarbons generated within the basin. The thorium occurs as thorite inclusions in the bitumen, and the development of the nodules was enhanced by the polymerization of fluid hydrocarbons by irradiation from the thorium. Thorium mobility may have been enhanced by the formation of organometallic complexes. Mineralization probably therefore occurred during hydrocarbon migration, dated as Late Carboniferous to Permian.     

甘孜—理塘结合带锰结核的发现及其地质意义

在甘孜—理塘结合带内理塘县中木拉乡附近发现锰结核。通过地质填图和综合研究,该锰结核产于结合带内瓦能蛇绿混杂岩组中的黑色粉砂质板岩中。其沉积层序为玄武岩→硅质岩→含锰结核粉砂质板岩。锰结核主量元素具有高Mn、低Fe、Si、Ca的特点,其中Mn含量为42.19%,高出大洋锰结核平均值1.83倍,Mn/Fe值较高,达8.1。锰结核中除Cr高于大洋锰结核平均值2～7倍外,多数微量元素低于大洋锰结核平均值。稀土元素具有较明显的Ce正异常,稀土总量、轻重稀土分异程度、Eu异常特征与混杂岩中的砂岩、硅质岩近似,而与玄武岩差别较大。该锰结核产出于大陆边缘构造环境,火山活动微弱,代表甘孜—理塘洋扩张到最大程度时的沉积。其时甘孜—理塘洋规模仍是有限的。     

The influence of metal content on the physical and mineralogical properties of pelagic manganese nodules

Deep sea manganese nodules are considered as important natural resources for the future because of their Ni, Cu and Co contents. Their different shapes cannot be correlated clearly with their chemical composition. Surface constitution, however, can be associated with the metal contents. A classification of the nodules is suggested on the basis of these results. The iron content of the nodules strikingly shows relations to the physical properties (e.g. density and porosity). The method of density-measurement is the reason for this covariance. The investigation of freeze-dried nodular substance does not give this result. The Fe-rich nodules lose more hydration water than the Fe-poor ones during heat drying. The reason for this effect is the different crystallinity, respectively the particle size. The mean particle size is calculated on the basis of geometrical models. The X-ray-diffraction analysis proves the variation of crystallinity in connection with the Fe-content, too. The internal nodular textures also show characteristic distinctions.     

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.     

深海锰结核中螺旋状超微生物化石的发现及其意义

对东太平洋深海瘤状锰结核透射电的系统观察和分析表明，瘤状锰结核的包壳，即奇异叠层石的建造者米级的螺旋状微生物、螺旋状微生物体的菌落呈圆盘状至不规则分枝状，菌落主下陷，营养菌丝体呈辐射状从中央向周围生长，营养菌丝体的束宽度为１７－６０ｎｍ，呈双分叉。生殖菌丝体由粗细不等的螺旋状丝体组成。螺旋状丝体的宽度３－２５ｎｍ，长度为３６－２００ｎｍ。螺环宽度为２－４ｎｍ、螺旋状生殖丝体分太、孢囊呈球形，深陷于     

Manganese Abnormity in Holocene Sediments of the Bohai Sea

Manganese abnormity has been observed in the Holocene sediments of the mud area of Bohai Sea. On the basis of grain size, chemical composition, heavy mineral content and accelerator mass spectrometry (AMS) 14C dating of foraminifer, relationships between manganese abnormity and sedimentation rates, material source, hydrodynamic conditions are probed. Manganese abnormity occurred during the Middle Holocene when sea level and sedimentation rates were higher than those at present. Sedimentary hiatus was not observed when material sources and hydrodynamic conditions were quite similar. Compared with the former period, the latter period showed a decrease in reduction environment and an inclination toward oxidation environment with high manganese content, whereas provenance and hydrodynamic conditions showed only a slight change. From the above observations, it can be concluded that correlation among manganese abnormity, material source, and hydrodynamic conditions is not obvious. Redox environment seems to be the key factor for manganese enrichment, which is mainly related to marine authigenic process.     

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。     

桃江锰矿锰帽形成的地球化学过程

桃江锰矿区发育有较完整的表生氧化剖面,根据不同深度矿石的结构构造,矿物组合及化学成分特征,将表生氧化剖面分成三个带：氧化矿石带,地渡矿石带和原生矿石带。桃江锰矿原生矿石矿物主要为含锰碳酸盐,表生富集作用包括两上地球化学过程;可溶杂质的溶解淋失作用和锰质的氧化残留作用。在过渡矿石带中,可溶性杂质发生大规模溶解迁移,锰质发生相对富集;氧化矿石带中,碳酸锰氧化成难溶的高价锰的氧化物,使锰质残留下来,形成     

Paleoceanographic Setting and Preservation of Buried Manganese Deposits in DSDP/ODP Cores

Abstract. The occurrence, lithology, and stratigraphic setting of buried manganese deposits and associated host sediments in cores obtained on Legs 123–210 of the Ocean Drilling Program (ODP) are examined in order to establish the formative environment and conditions of preservation. Fossil manganese nodule and crusts are found to have formed or deposited throughout the period from 100 Ma to the present, with an additional example of formation near 137 Ma, suggesting that the deep-sea environment has been oxic and suitable for the formation of manganese nodules and crusts since the Cretaceous. Many manganese nodules and crusts occur on horizons corresponding to hiatuses in sedimentation or periods of slow sedimentation, consistent with the environment in which modern nodules form (sedimentation rate less than 10 m/m.y.). Sediments overlying the fossil nodules and crusts are oozes or biogenic sediments with sedimentation rates of 1–18 m/m.y. Low total organic carbon (<0.1 wt%) in the overlying sediments and high sulfate content (>25 mM) in interstitial water around the manganese horizon suggest that no strong reduction occurred within the overlying sediments. Coverage by biogenic sediments containing only small amounts of organic matter is therefore considered important for the preservation of manganese nodules and crusts. Manganese carbonate occurs sporadically as nodules, concretions or thin layers in various host sediments, including clay, calcareous ooze and siliceous ooze with sedimentation rates of 6–125 m/m.y. Hiatuses are rare around the host sediments of manganese carbonate. Higher total organic carbon (0.2–1.8 wt%) in the host sediments and lower sulfate content (0–25 mM) in interstitial water around the manganese carbonate horizon suggest that reduction in association with decomposition of organic matter would have proceeded in the host sediments.     

Biogenic signature and ultra microfossils in ferromanganese nodules of the Central Indian Ocean Basin

Theories related to the precipitation mechanism of the metallic elements in marine manganese nodules have remained controversial between two schools of thoughts (1) chemical oxidation (abiotic origin) and (2) deposition of the metals through microbial enzymatic processes (biogenic origin). One of the most important evidence in support of the biogenic origin is the occurrence of fossilized microbes. However, well-documented literature in this regard is either lacking or very scanty in case of Indian Ocean nodules. Using high resolution FEG-SEM we have recorded various biogenic signatures and ultra microfossils in the ferromanganese nodule samples from Central Indian Ocean Basin (CIOB) that are presented in this paper. The microfossils are mostly protozoans belonging to varieties of bacteria, diatoms and foraminifera. Some of the features recorded in this study have perhaps never been reported before from any manganese nodules. The chemical compositions of these ultra microfossils indicate a high-level of manganese precipitation in and around them in comparison to the distant surrounding areas. While clumpy microbes are enriched with nickel, the rod shaped bacteria are rich in copper. Up to 4.70 wt.% nickel and 5.31 wt.% Cu have been recorded in the fossilized microbe bodies. The high abundance of biogenic features as well as microfossils in the ferromanganese nodules and their chemical compositions support arguments in favor of a dominant role of the microorganisms in the construction of the nodules of the CIOB.     

The Indian Ocean Nodule Field: petrotectonic evolution and ferromanganese deposits

The Indian Ocean Nodule Field (IONF) is significant from several points of view. Roughly bordered by 10°S to 16°30′S and 72°E to 80°E and located within the Central Indian Ocean Basin (CIOB), the field hosts the world's second largest and second high grade manganese nodule deposit, after the equatorial nodule belt in the north Pacific Ocean. Moreover, the crust underlying this field is characterised by unique morphotectonic signatures owing to its formation between 60 and 49 Ma under three variable spreading conditions, fast, intermediate and slow, from the Indian Ocean Ridge System (IORS).The nodule field has been surveyed both extensively (more than 0.4 million km² area) and intensively (comprising of a large geophysical data set and geological sample inventory) during the last two decades. Several morphotectonic features, such as seamounts, hills, ridge-normal lineaments and ridge-parallel lineations, have disturbed the apparently smooth topographic gradient (1:7000) of the seafloor here.Variations in the rate of spreading and formation of new oceanic crust along the ridge crest, during more than one episode of India–Eurasia collision, are imprinted in the IONF. Based on the nature of the ridge-parallel lineations, which are related to the rate of crustal accretion, the field is divided in to four sectors: A, B, C, and D, from north to south. Sectors A and C were formed at a fast rate of spreading (90–95 mm/year, half-rate) and sectors B and D were formed at an intermediate (55 mm/year) and slow (26 mm/year) rates, respectively. The predominance of tensional stress in sectors A and C caused asymmetrical flexuring of the seafloor, resulting in widely spaced faults and folds with low amplitude and large wavelength. In contrast, the seafloor flexuring in sector D are closely spaced, long, symmetrical and of high amplitude. The timing and intensity of the collision of India with Eurasia is constrained by the variable intensity of these flexures, suggesting probably a ‘soft’ touch at ∼58 Ma and the hard collision at about 51 Ma.The nodule field hosts several seamounts, both as isolated entities and in linear chains, which are arranged parallel to the flow lines along the direction of absolute motion of the Indian plate. The distribution, morphology and growth patterns of a majority of these seamounts are related to spreading rate, suggesting their formation at the ridge crest. However, many of the seamounts show more than one stage of growth with local intraplate volcanism contributing to the enlargement of the larger ancient seamounts. Varieties of volcanics, such as tholeiitic basalts, spilites, ferrobasalts and pumice, occur within the IONF. The alteration of some of these volcanics has resulted in palagonitisation of the glass and formation of zeolites.Subsequently, during its journey away from the ridge crest to the abyssal areas, the crust underlying the nodule field witnessed intraplate volcanism. This is evident from the addition of younger rocks at the base of the ancient seamounts, inconsistent growth of volcanoes, eruption of ferrobasalt corresponding to the areas of high amplitude magnetic zones and presence of volcanogenic–hydrothermal materials (vhm) of 10 ka age. These findings collectively hint that the IONF is geodynamically unstable and may have been volcanically active in the recent past.During the last 8 Ma, growth of authigenic ferromanganese deposits in the form of manganese nodules and crusts has occurred in the nodule field. The deposits occur at an average water depth of 5000 m. The basinal geomorphology, intraplate tectonic deformations and volcanic eruptions considerably influence the formation, development, morphology, mineralogy and composition of these deposits. The data show that the large seamounts, reverse faults and fracture zones (FZs) supply rock fragments as ‘seeds’ for the nodule formation. The hydrogenous precipitation from the overlying water column is the primary source of metal accumulation in the nodules. The secondary (relatively weak) intraplate eruptions along the base of ancient seamounts or lineaments, subsurface igneous activity and diagenetic remobilisation of metals have also played significant role in the growth and enrichment of the deposit.Based on a large data set, we estimate the contribution of various physico-chemical parameters and model the probable conditions of formation of the ferromanganese deposits in the IONF. The model also hints at the location where the resource exploitation should be rewarding.