Variations in the elemental composition of ferromanganese structures from Lake Baikal

The elemental composition of ferromanganese sedimentary structures from the bottom of Lake Baikal represented by nodules and crusts, as well as the enclosing sediments, have been studied by the atomic absorption, chemical, and ICP-MS methods. It is established that the contents of the rock-forming and accompanying elements in them are highly variable. In this connection, the examined samples are divided in two groups differing by their Mn/Fe values. In most of the samples, they range from 0.01 to 0.1, although some of the ferromanganese structures or their parts are substantially enriched in manganese. The contents of most of the rare and dispersed elements in the ferromanganese structures are usually at the background level, although the samples maximally enriched in iron or manganese are characterized by relatively high copper, nickel, cobalt, vanadium, zinc, and molybdenum concentrations.     

A comparative analysis of compositional variations in and between marine ferromanganese nodules and crusts in the South Pacific and their environmental controls

Regional variation of Mn, Fe, Co, Ni and Cu in ferromanganese oxides (nodules and crusts) in the central south Pacific is related to primary productivity, oxygen minimum layer, and calcium carbonate compensation depth. The largely latitudinal influence of these environmental parameters on nodule and crust composition reflects their predominantly latitudinal variation. Primary productivity is the principal regional environmental control, influencing diagenetic enrichment of these elements in nodules through its effect, mediated by the CCD, on supply and concentration of labile organic matter vs. carbonate remains to the sediments. It influences hydrogenetic enrichment of these elements in nodules and crusts through its effect, mediated by the oxygen minimum layer (mainly in the case of crusts), on their export from surface waters.The elements’ varying susceptibility to being scavenged or organically bound influences the contrasting composition of diagenetic vs. hydrogenetic ferromanganese oxides, which is further influenced by depth. Hydrogenesis is the fundamental process governing nodule and crust formation, superimposed on which is diagenesis under specific circumstances; both are subject to intermittent interruption, diminution and augmentation by changes in environmental parameters. Application of regionally operative environmental controls locally explains local compositional variations and helps refine exploration criteria for economically viable nodules and crusts.     

Structure and composition of the consolidated mud tube of Maldane sarsi (Polychaeta: Maldanidae)

Maldanid polychaetes can be important components of marine benthic communities, playing significant roles in particle subduction or sediment irrigation. Many maldanids are known to inhabit tubes consisting of sediments consolidated by mucus; the structure and composition of these tubes, and their potential impact on benthic environments, are poorly known. We examined the three-dimensional organization of Maldane sarsi tubes, using CT scanning together with analyses of sediment grain size and concentrations of Fe, Mn, organic carbon and bacteria in tube material. M. sarsi tubes consist of stacks of individual consolidated mud disks, surrounding a dense, continuous, inner tube. The tubes of M. sarsi contained fewer fine particles than surrounding sediments, and greater concentrations of Fe, Mn, organic carbon and bacteria, especially in the inner zone. These distributions suggest that tube irrigation affects Fe and Mn oxidation and precipitation in a narrow zone surrounding M. sarsi, and that mucous secretion and potential feeding activities (the hoeing of surface sediments) lead to increases in organic carbon and bacteria in the inner, and deepest parts of the tube. The finding of relict tubes, buried at up to 15 cm depth, indicates a relatively high longevity for these structures and suggests a potential importance in biogeochemical cycling.     

Minor and rare elements in manganese crusts and nodules and sediments from the Manihiki plateau and adjacent areas: Results of HMNZS Tui cruises

Six manganese crusts, 13 manganese nodules, and 16 sediments were analyzed by instrumental neutron activation analysis. Data were generated on selected major and minor elements but geochemical evaluations are based only on Fe, Sc, U, Th, and the rare earth elements (REE). Manganese crusts and manganese nodules have comparable trivalent REE contents and show a shale‐like distribution pattern. Both crusts and nodules are characterized by a positive Ce anomaly but the anomaly is higher in nodules. REE contents in manganese nodules show a linear dependence on the Fe content, and it is concluded that these elements are incorporated in the Fe‐rich (δ‐MnO₂) phase. In the crusts, the REE correlate with Sc and are therefore assumed to be associated with the clay minerals. Uranium contents are significantly higher in the crusts than in nodules whereas Th is slightly higher in the nodules. There is a clear positive correlation between U and Th in nodules but there are too few data to make a similar conclusion for crusts. Compositional data suggest a division of the sediments into two groups. The carbonate sediments have much lower REE contents and a more pronounced negative Ce anomaly than the clays, while both show a lithogenous component as indicated by a slight negative Eu anomaly.     

Geochemical tracers of northern Portuguese estuarine sediments on the shelf

The northern Portuguese coastal zone is drained by large Iberian rivers, along which there is intensive industrial, agricultural and urban activity. Offshore of the two main river basins of the Douro and Minho, two fine-grained sedimentary formations can be characterised. A geochemical study of this sediment cover has been performed focussing in particular on the fine deposits and the adjacent estuaries. The chemical composition of superficial sediments collected from the northern Portuguese shelf and from the river basins of the Minho and Douro rivers was determined for major, minor and trace elements; the rare earth elements (REE) composition was also determined in selected samples. Statistical analyses of these data for the shelf sediments allow us to identify elements with similar behaviours and the different sediment types along the shelf, and to evaluate of their origins. Downcore profiles of the chemical composition of the fine sediments reveal no evidence for changes induced by recent human activities. To assess the influence of the rivers on the fine sedimentary formations, the elemental distribution patterns of selected sediments have been compared with the estuarine sediments. Lithogenic elements composition normalised to Al and the shale normalised REE distributions showed there are similarities between the Douro River sediments and the sediment composition of the Douro and Galicia mud patches. However, the Galicia mud field showed no relationship in its chemical composition to sediments derived from the Minho River. Nor was any evidence for heavy metal contamination originating from the Douro estuary detected in anthropogenic element/Al ratios in the shelf sediments. This may be because of processes associated with resuspension, complexation and bioturbation that occur during sediment transport and deposition. Nevertheless, the Douro River seems to be the main continental source of fine sediments being deposited on the northern Portuguese shelf.     

中太平洋富钴结壳中生物标志物、有机碳同位素地球化学及其古海洋环境意义

利用2003年大洋DY105-12,14航次在中太平洋海山获取的KXD28富钴结壳样品,采用气相色谱(GC)内标法对该结壳样品的分层样进行了可溶有机质(氯仿沥青“A”)及其族组成(饱和烃、芳烃、非烃)、正构烷烃、类异戊二烯烃的定量分析,并结合总有机碳(TOC)及有机碳同位素(δ¹³C)分析,探讨了结壳样品有机质来源及富钴结壳组成与生长环境之间的关系。结果表明:(1)富钴结壳中有机质生物母源主要为海洋生物和菌藻类,并混有少量陆源物质;有机碳同位素同样也指示了海洋水生生物碳同位素特征;(2)KXD28结壳从底层到最外层有机碳同位素发生了很大变化,结壳中有机碳同位素组成变化与结壳生长过程中的海洋环境气候相符合:富钴结壳生长前期δ¹³C组成由正变负,对应全球气候变冷,南极底层流向太平洋挺进;而富钴结壳生长后期δ¹³C逐渐偏正,与全球气候变暖和南极底层流萎缩相关联。     

Composition and Useful Properties of Tailings of Marine Manganese Nodules and Crusts

ABSTRACT

Marine manganese nodules and crusts, when processed, yield tailings which may be utilized for environmental and economic benefit. The key to the reasonable and effective utilization of these tailings lies in making a systematic appraisal of their composition and properties. This article gives an introduction to the investigation of manganese tailings properties. The tailings have a high iron and/or manganese content, high surface area, high porosity, and fine grain size. Some tailings have a high rare earth element content which is valuable. They may also have high SO₃, arsenic, and uranium contents which are harmful. Depending on the process used to produce the tailings, there will likely be some differences in chemical composition, mineral assemblages, surface area and adsorption capability, pore diameter and volume, density and pH. In assigning potentially beneficial applications for these tailings, these differences should be taken into account to optimize utilization.     

南海铁锰结核(壳)的地球化学特征

本文研究了南海中部铁锰结核(壳)的地球化学特征。南海铁锰结核(壳)以高Mn富Ni为特征。但不同沉积部位的铁锰结核(壳),化学成分也有一定的差异,这是受不同沉积区的物源特性,地化环境差异和沉积成矿过程中环境的变化所影响的结果。     

大洋铁锰结壳的地球化学与古海洋环境示踪

主要回顾近年来铁锰结壳在深度定年、主量元素、微量元素及Sr，Nd，Pb同位素地球化学及其古海洋环境示踪方面的主要研究进展，并提出有关认识和展望。     

Element composition of ferromanganese concretions in the Black Sea

The ferromanganese concretions spread at the bottom of the shallow northwestern part of the Black Sea are mainly represented by Fe and Mn hydrate nodules on shells and substituted worm tubes. The element composition of these formations was found by the methods of chemical, atomic-absorbtion, neutron activation, and plasmic (ICP-MS) analyses. It is established that the content and the ratio of Fe and Mn in the concretions ranges within considerable limits, which controls the occurrence of several associated iron-free metals and microelements, some which have not been previously studied in the Black Sea concretions.     

Controls on regional variability in marine pore-water diagenesis below the seafloor in Upper Jurassic–Lower Cretaceous prodeltaic sandstone and shales,Scotian Basin,Eastern Canada

Diagenesis in the uppermost Jurassic to Lower Cretaceous deltaic sandstones and shales of the Scotian Basin is an important control on reservoir quality. Ferruginous zone (sub-oxic) marine pore-water diagenesis controls the initial formation of Fe²⁺-silicates that are the precursors of grain-rimming chlorite that preserves porosity. This study assesses the regional controls on the type of marine pore-water diagenesis by studying the sedimentology, mineralogy, and geochemistry of the retrogradational units and underlying progradational units in parasequences from conventional cores in two wells in different parts of the basin. Coated grains preserve a record of whether marine pore-water diagenesis below the seafloor was dominantly in the ferruginous or sulphidic geochemical zone. Four types of coated grain were distinguished, each with a different mineral paragenesis. Mineralogical and chemical evidence of ferruginous zone diagenesis includes the presence of diagenetic chlorite and siderite, and the correlation of P with Fe or Ti. Pyrite and Fe-calcite are found where the sulphidic zone is more significant than the ferruginous zone. Ferruginous zone diagenesis was common in low-sedimentation rate retrogradational sediments with low organic carbon, and in delta-front turbidites and river-mouth sandstones. Estuarine, tidal flat and prodeltaic facies that are directly supplied by riverine sediments have a lower Fe:Ti ratio than do fully marine shoreface and open shelf facies as a result of input of detrital ilmenite and its alteration products. The relative contribution of colloidal iron (hydr)-oxides appears greater in distal low-sedimentation rate environments. Where large changes in sedimentation rate occurred at ravinement surfaces, the underlying progradational rocks have evidence of ferruginous zone diagenesis, whatever their facies. Rapid upward migration of the pore-water profile resulting from the change in sedimentation rate reduced the time available for mineral products to form in the deeper pore-water zones. This study has shown that the availability of Fe and organic carbon varying in a complex manner in marine deltaic sediments, but that the resulting diagenesis by marine pore-water can be predicted from facies and paleogeographic setting.     

Composition and Useful Properties of Tailings of Marine Manganese Nodules and Crusts

Marine manganese nodules and crusts, when processed, yield tailings which may be utilized for environmental and economic benefit. The key to the reasonable and effective utilization of these tailings lies in making a systematic appraisal of their composition and properties. This article gives an introduction to the investigation of manganese tailings properties. The tailings have a high iron and/or manganese content, high surface area, high porosity, and fine grain size. Some tailings have a high rare earth element content which is valuable. They may also have high SO₃, arsenic, and uranium contents which are harmful. Depending on the process used to produce the tailings, there will likely be some differences in chemical composition, mineral assemblages, surface area and adsorption capability, pore diameter and volume, density and pH. In assigning potentially beneficial applications for these tailings, these differences should be taken into account to optimize utilization.     

Marine barite in sediments from deep sea drilling project sites 424 and 424a (Galapagos hydrothermal mounds field)

The distribution of barite in sediments from D.S.D.P. sites 424 and 424A at the Galapagos hydrothermal mounds field is determined and the process of its formation is deduced. Barite in these deposits is associated with calcareous sediments and is completely absent from the hydrothermal material (manganese crusts and nontronite). Its concentrations tend to increase in the deeper sediments. Since manganese crusts contain significant amounts of Ba, a lack of barite in them is probably due to low concentrations of SO₄² in the sediment-seawater interface where they form. The formation of barite occurs within buried sediments, the interstitial waters of which are saturated with SO₄². The most probable source of SO₄²⁻ is the oxidation of H₂S which is released from the hydrothermal fluids percolating upwards through the sediments. Although nontronite is formed within buried sediments the environmental conditions occurring during its formation (reducing) prevent barite formation.The association of barite with calcareous sediments is due to the release of Ba by calcareous microorganisms and/or to high concentrations of Ca in the pore waters which maintain a high pH and hence SO₄²⁻ is stable.     

Morphological Features of Co-Rich Manganese Deposits and Their Relation to Seabed Slopes

Abstract

The morphological features associated with Co-rich manganese deposits, the size variations of nodules, and the occurrence of different substrates have been analyzed, to evaluate the influence of various seabed slope angles on the distribution of these features. The coverage and size of the crusts depend on their surface morphology and seabed topography, resulting in cobble-type, lineated, or step-like outcrops. Small nodules (1–4 cm in diameter) dominate all seabed slopes, with a few locations having nodules ranging from 1 to 8 or 1 to 10 cm. Sediments invariably occur as substrates for nodules and as cover for crusts, their coverage being inversely proportional to that of the nodules and crust outcrops.

Steeper seafloor areas have large crust outcrops exposed with no or few nodules and sediments associated with them. The intermediate slopes have a combination of nodules, sediments, and crusts in various proportions, depending on topography and gradient. Large-scale nodule occurrences, followed by sediment fields and crust outcrops on seabed slopes of < 3°, 3–7°, and > 15°, respectively, represent typical morphological distribution zones of the Co-rich manganese deposits on a seamount in the central Pacific Ocean. A transition zone between nodule-dominated fields and large crust outcrops occurs for slopes from 7° to 15°. This detailed study on distribution of Co-rich deposits gives a better understanding for purposes of their exploitation.     

Authigenic carbonates from methane seeps of the Congo deep-sea fan

Submersible investigations with the ROV Victor 6000 of some pockmark structures on the seafloor of the Congo deep-sea fan have shown that they are active venting sites of methane-rich fluids, associated with abundant fauna and carbonate crusts. Moreover, methane hydrates have been observed both outcropping and deep in the sediments in the centre of the “Regab” giant pockmark. Authigenic carbonates, mostly calcite sometimes mixed with aragonite, are cementing the sedimentary matrix components and fauna; diatoms are abundant but only as moulds, indicating that biogenic silica dissolution occurred in situ synchronous with carbonate precipitation. The occurrence of diagenetic barite and pyrite in some carbonate crusts demonstrates that they can be formed either within the sulphate/methane transition zone or deeper in sulphate-depleted sediments. The oxygen isotopic compositions of the diagenetic carbonates (3.17–6.01‰ V-PDB) indicate that precipitation occurred with bottom seawater mixed with a variable contribution of water from gas hydrate decomposition. The very low carbon isotopic compositions of the diagenetic carbonates (−57.1 to −27.75‰ V-PDB) demonstrate that carbon derives mostly from the microbial oxidation of methane.     

Submersible observations of manganese nodule and crust deposits on the Tenpo Seamount,Northwestern Pacific

Pavements of manganese nodules and crusts and outcrops of Miocene limestones were observed on the flanks and flat top of the Tenpo Seamount during three Shinkai 2000 dives. The pre‐Miocene volcano supplied nuclei of volcanic rocks and hydrothermal manganese deposits, and subsequent slow or no sedimentation promoted deposition of abundant hydrogenetic nodules and crusts, mainly on the upper flank of the seamount. Nodule pavements generally cover calcareous sand surface sediments, while crusts cover hard outcrops composed probably of volcanic rocks. The fields of crusts and nodules are sparsely distributed with each other on scales of meters to tens of meters. The on‐site observation suggests the deposits have encountered tectonic and/or mass movements that resulted in unusual occurrences of densely stacked nodules and occasionally the nodules resting directly on crusts or hard substrates. Mineralogical and chemical compositions reveal that for nodules and crusts the encrusting manganese layers of around 1 cm thickness are composed of hydrogenetic vernadite, and diagenetic influence is negligible.     

东菲律宾海表层沉积物中元素的赋存状态

为了解东菲律宾海不同类型表层沉积物中元素的赋存状态,采用化学提取方法对有无新型铁锰结壳发育站位表层沉积物样品进行了分级提取及测试,不同类型表层沉积物中成矿和稀土元素的赋存状态总体一致,表明研究区表层沉积物形成于相似的地质和海洋环境中。成矿元素中Fe绝大部分赋存在残渣态中,Mn、Cu、Co和Ni则主要赋存在铁锰氧化物结合态中,稀土元素也主要赋存在这两个相态中,碳酸盐结合态、铁锰氧化物结合态和有机结合态对重稀土元素优先吸附或具络合作用,引起重稀土元素的相对富集和铈的负异常,残渣态优先吸附轻稀土元素,导致轻稀土元素的富集和铈的正异常,火山物质则使表层沉积物残渣态表现出铕的正异常特征。同时,不同表层沉积物样品间也存在一定的差异,这与其局部形成条件——铁锰结壳发育与否有关。     

Composition and secondary alterations of microfossils in sediments of the Ashadze-1 hydrothermal field (tropical Mid-Atlantic Ridge)

The first thorough analysis of microfossils from ore-bearing sediments of the Ashadze-1 hydrothermal field in the Mid-Atlantic Ridge sampled during cruise 26 of the R/V Professor Logachev in 2005 revealed the substantial influence of hydrothermal processes on the preservation of planktonic calcareous organisms, as well as on the preservation and composition of the benthic foraminifers. From the lateral and vertical distribution patterns and the secondary alterations of the microfossils, it is inferred that the main phase of the hydrothermal mineralization occurred in the Holocene. Heavy metals (Cu, Co, Cr, and Ag) were accumulated by foraminiferal tests and in their enveloping Fe-Mn crusts. The distribution of authigenic minerals replacing foraminiferal tests demonstrates local zoning related to the hydrothermal activity. There are three mineral-geochemical zones defined: the sulfide zone, the zone with an elevated Mg content, and zone of Fe-Mn crusts.     

全球海洋地球化学调查进展

地球化学参数是与气候、环境、生态、资源等关系最为密切的指标之一,过去几十年中在矿产资源勘查、环境保护等领域得到了充分应用。海洋地球化学调查和研究工作也在不断深入,但缺少类似陆地地球化学填图那样系统的专项工作,对全球海洋资源、环境的评估与研究的支撑作用仍不够明显,元素含量及同位素组成等在全球海洋中的分布趋势仍认识不足。笔者对全球海洋沉积物、岩石、结核结壳和水体的无机地球化学调查进展进行了系统梳理,全面介绍了目前已开展的工作和取得的主要成果,以期为全球尺度地球化学研究提供重要参考。     

Morphological Features of Co-Rich Manganese Deposits and Their Relation to Seabed Slopes

The morphological features associated with Co-rich manganese deposits, the size variations of nodules, and the occurrence of different substrates have been analyzed, to evaluate the influence of various seabed slope angles on the distribution of these features. The coverage and size of the crusts depend on their surface morphology and seabed topography, resulting in cobble-type, lineated, or step-like outcrops. Small nodules (1 - 4 cm in diameter) dominate all seabed slopes, with a few locations having nodules ranging from 1 to 8 or 1 to 10 cm. Sediments invariably occur as substrates for nodules and as cover for crusts, their coverage being inversely proportional to that of the nodules and crust outcrops. Steeper seafloor areas have large crust outcrops exposed with no or few nodules and sediments associated with them. The intermediate slopes have a combination of nodules, sediments, and crusts in various proportions, depending on topography and gradient. Large-scale nodule occurrences, followed by sediment fields and crust outcrops on seabed slopes of greater than 3 degrees, 3 - 7 degreees, and less than 15 degrees, respectively, represent typical morphological distribution zones of the Co-rich manganese deposits on a seamount in the central Pacific Ocean. A transition zone between nodule-dominated fields and large crust outcrops occurs for slopes from 7 degrees to 15 degrees. This detailed study on distribution of Co-rich deposits gives a better understanding for purposes of their exploitation.