Ferromanganese oxide deposits from the Central Pacific Ocean,II. Nodules and associated sediments

Bulk chemical, mineralogical and selective leach analyses have been made on a suite of abyssal ferromanganese nodules and associated sediments from the S.W. equatorial Pacific Ocean. Compositional relations between nodules, sediment oxyhydroxides and nearby ferromanganese encrustations are drawn assuming that the crusts represent purely hydrogenetic ferromanganese material. Crusts, δMnO₂-rich nodules and sediment oxyhydroxides are compositionally similar and distinct from diagenetic todorokitebearing nodules. Compared to Fe-Mn crusts, sediment oxyhydroxides are however slightly enriched, relative to Mn and Ni, in Fe, Cu, Zn, Ti and Al, and depleted in Co and Pb, reflecting processes of non-hydrogenous element supply and diagenesis. δMnO₂ nodules exhibit compositions intermediate between Fe-Mn crusts and sediment oxyhydroxides and thus are considered to accrete oxides from both the water column and associated sediments.Deep ocean vertical element fluxes associated with large organic aggregates, biogenic calcite, silica and soft parts have been calculated for the study area. Fluxes associated with organic aggregates are one to three orders of magnitude greater than those associated with the other phases considered, are in good agreement with element accumulation rates in sediments, and are up to four orders of magnitude greater than element accumulation rates in nodules. Metal release from labile biogenic material in surface sediments can qualitatively explain the differences between the composition of Fe-Mn crusts and sediment oxyhydroxides.Todorokite-rich diagenetic nodules are confined to an eastwards widening equatorial wedge. It is proposed that todorokite precipitates directly from interstitial waters. Since the transition metal chemistry of interstitial waters is controlled dominantly by reactions involving the breakdown of organic carbon, the supply and degradation rate of organic material is a critical factor in the formation of diagenetic nodules. The wide range of (trace metal/Mn) ratios observed in marine todorokite reflects a balance between the release of trace metals from labile biogenic phases and the reductive remobilisation of Mn oxide, both of which are related to the breakdown of organic carbon.     

Playa‐lake sedimentation and organic matter accumulation in an Andean piggyback basin: the recent record from the Cuenca de Pozuelos,North‐west Argentina

Expansive playa‐lake systems situated in high‐altitude piggyback basins are important and conspicuous components of both modern and ancient cordilleran orogenic systems. Extant playa lakes provide vital habitat for numerous endemic species, whereas sediments from these deposystems may record signals of climate change or develop natural resources over geological time. Laguna de los Pozuelos (North‐west Argentina) provides the opportunity for an actualistic sedimentological and geochemical assessment of a piggyback basin playa lake in an area of critical interest for understanding Quaternary palaeoclimate dynamics. Silty clays and diatom ooze are the dominant playa‐lake centre microfacies, with concentrations of total organic carbon and biogenic silica commonly exceeding 1·5 wt% in this sub‐environment. Elemental and stable isotopic analyses point to a mixed organic matter composition in the playa‐lake centre, with substantial contributions from algae and transported aquatic macrophytes. Bulk sediment and organic mass accumulation rates in the southern playa‐lake centre approach 0·22 g cm^?2 year^?1 and 2·89 mg cm^?2 year^?1, respectively, indicating moderately rapid deposition with negligible deflation over historic time. Playa margin facies contain higher percentages of fragmented biogenic carbonate (ostracods and charophytes) and inorganically precipitated aragonite crusts due to seasonal pumping and evaporation of ground water. Organic matter accumulation is limited along these heavily bioturbated wet and dry mud flats. Fluvial–lacustrine transitional environments, which are key waterbird habitats, are either silty terminal splay (northern axis) or sandy deltas (southern axis) containing highly oxidized and partially allochthonous organic matter. Modern analogue data from Laguna de los Pozuelos provide key insights for: (i) environmental reconstructions of ancient lake sequences; and (ii) improving facies models for piggyback basins.     

初论发现于西太平洋富钴结壳的羟锰矿

大多数研究者认为富钴结壳中的锰矿物主要是水羟锰矿。X-射线衍射数据表明这次所研究的富钴结壳中主要的富锰矿物相是羟锰矿,这是在以往的结核和结壳研究中鲜为人知。探讨了羟锰矿和水羟锰矿的名称由来、化学式、晶胞参数及X射线粉晶衍射值,建议将X-射线衍射特征值为2.4×10^-10 m和1.4×10^-10 m的锰矿物相统称为水羟锰矿;通过研究这两种矿物的成因、产状及环境,认为结壳中羟锰矿的存在表明结壳在生长中后阶段仍处于还原环境。     

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.     

Early submarine cementation in fore-reef carbonate sediments, Barbados, West Indies

Bottom sediments from the sea floor west of Barbados between depths of 110 and 324 m are composed of nodular or crusted carbonate deposits. Individual biogenic sediment grains and the cemented aggregates, nodules and crusts are usually more or less altered by bioerosion and may support one or more generations of encrusting organisms. On the basis of component analysis of the topmost part of the bottom sediments it is possible to recognize three facies: (1) a proximal slope facies down to a depth of about 140 m, rich in mollusc fragments, benthic foraminifera and bryozoans; (2) an upper distal slope facies between about 140 m and about 215 m, rich in benthic foraminifera, molluses and crustaceans; and (3) a lower distal slope facies from about 215 m to at least 300 m, dominated by molluscs, especially pelecypods, with subordinate scleractinians and tubes of the polychaete Lygdamus asteriformis. The appearance and quantitative importance of the cemented aggregates is also related to these facles. In the proximal slope facies, only relatively few irregular and very porous nodules are found, whereas in the lower distal slope facies, aggregates are very common. Most aggregates are crust-like with a smooth upper surface and a more or less irregular, knobby lower surface. The crusts are massive compared with the nodules of the proximal slope facies and, unlike the latter, the lower surfaces and walls of larger cavities are usually coated with Fe and/or Mn oxides. In the upper distal slope facies a gradual transition between the two types of aggregates is found. Petrographical and morphological evidence, together with carbon and oxygen isotopic data, indicates that the nodules and crusts were formed in situ by submarine lithification processes. Radiocarbon dating of two bulk samples suggests that the cementation took place during late Pleistocene and/or early Holocene.     

Geochemistry of trace and minor elements in sediments and manganese micronodules from the Angola Basin

Indicator role of trace elements in sedimentation and ore formation is considered for sediments from Station 2182 in the Angola Basin. It is shown that pelagic sediments were formed from two main sources: biogenic calcium carbonate and lithogenic sediment component compositionally similar to the miopelagic clay. Increase of the Mn/Al ratio, Ce anomaly in the REE composition, Co/Ni and Mo/W ratios, and anomalous accumulation of Tl, Pb, Bi and other microelements indicate that sediments from horizons 15–20 and 30–35 cm contain significant amounts of hydrogenic material as Fe-Mn oxyhydroxides. Manganese micronodules (MN) were extracted from different horizons (10–15, 15–20, and 30–35 cm) and analyzed to study the hydrogenic component. Their development is related to retardation of biogenic and lithogenic sedimentation. The studied manganese micronodules are represented by the hydrogenic-diagenetic formations >100 μm in size with Mn/Fe = 2.0–2.8, Co/Ni = 0.2–0.4, Ce an = 4.2–5.7, and Mo/W = 5.2–7.9. The MN content is too low to affect the major and trace element composition of sediments. The main part of Fe and Mn is confined to fraction <10 μm.     

万山特区铁门闩碳酸锰矿床特征及成因浅析

铁门闩碳酸锰矿受控于地层层位,呈层状,似层状、透镜状沿震旦系下统大塘坡组一段（Ｚ１ｄ）富含有机质炭质页岩下部顺层产出。根据含锰岩系特征,矿体形态规模,矿石质量的分析研究,该锰矿床应属浅海沉积型碳酸锰矿。     

Growth Rate Estimates of Supergene Manganese Nodule by^40Ar／^39Ar Isotopic Dating

INTRODUCTIONModern4 0 Ar/ 39Arlaserstep heatinganalysishasbeensuccessfullyappliedtodateverysmallmineralgrainsfromdiversegeologicalenvironments .Thefineresolutionofthismethodhasgreatlyhelpovercomeproblemsintrinsicintradi tionalK Armethod ,inducedbyexcessargon ,argonlossbythermalresetting ,39Arrecoilduringirradiation ,andinter growthsand/orcontaminationofdifferentgenerationminer als ,withintheanalyzedmineral (Smithetal.,1998;Vas concelosetal.,1994 ) .Supergenemanganeseoredepositsareeconom…     

太平洋西北平顶海山上环礁型碳酸盐建造与白垩纪赤道洋流

深海钻探揭示构成环礁的浅水碳酸盐建隆覆盖沉积在太平洋西北部平顶海山之上。相对于现今珊瑚藻类生物构成的环礁而言,白垩纪和古新世孤立的环礁的四周边缘生物含量甚少,造礁能力下降。这些环礁浅水碳酸盐沉积在火山基座的顶部,在Albian初期、Albian末期、Maastrichtian晚期和始新世中期发生沉没。早期研究认为这些碳酸盐体系经历了地面暴露阶段以及随后的海侵淹没阶段。然而,一个事实是,环礁沉没仅发生在当太平洋板块背负着平顶海山向北漂移过程中,并且是经过南纬7°以后。几个不同的假说用来解释该时期环礁沉没现象,包括环礁暴露、喀斯特化、地面侵蚀、增强赤道上升洋流、缺氧和/或者富营养的浑浊水的出现等。文中在太平洋平顶海山深海钻孔的沉积、生物地层和古纬度数据综合研究基础上,提出一种新模式用于解释晚白垩世—古新世浅水碳酸盐建造的沉没。与以前的模式不同的是,文中提出,这些晚白垩世—古新世“环礁”之所以发生沉没,原因是受到原始环南赤道洋流(pSEC)的影响,导致一种对分泌碳酸盐的生物不利环境的产生。而且,当这些平顶海山漂移到南纬5°时,即赤道古纬度带,许多浅水碳酸盐建造之上,铁锰结核开始沉积。同时,平顶海山下沉到溶解氧极小层(海平面之下400~1 100 m)和原始环南赤道中层洋流( pEI     

Sedimentary manganese metallogenesis in response to the evolution of the Earth system

The concentration of manganese in solution and its precipitation in inorganic systems are primarily redox-controlled, guided by several Earth processes most of which were tectonically induced. The Early Archean atmosphere-hydrosphere system was extremely O₂-deficient. Thus, the very high mantle heat flux producing superplumes, severe outgassing and high-temperature hydrothermal activity introduced substantial Mn²⁺ in anoxic oceans but prevented its precipitation. During the Late Archean, centered at ca. 2.75 Ga, the introduction of Photosystem II and decrease of the oxygen sinks led to a limited buildup of surface O₂-content locally, initiating modest deposition of manganese in shallow basin-margin oxygenated niches (e.g., deposits in India and Brazil). Rapid burial of organic matter, decline of reduced gases from a progressively oxygenated mantle and a net increase in photosynthetic oxygen marked the Archean-Proterozoic transition. Concurrently, a massive drawdown of atmospheric CO₂ owing to increased weathering rates on the tectonically expanded freeboard of the assembled supercontinents caused Paleoproterozoic glaciations (2.45-2.22 Ga). The spectacular sedimentary manganese deposits (at ca. 2.4 Ga) of Transvaal Supergroup, South Africa, were formed by oxidation of hydrothermally derived Mn²⁺ transferred from a stratified ocean to the continental shelf by transgression. Episodes of increased burial rate of organic matter during ca. 2.4 and 2.06 Ga are correlatable to ocean stratification and further rise of oxygen in the atmosphere. Black shale-hosted Mn carbonate deposits in the Birimian sequence (ca. 2.3-2.0 Ga), West Africa, its equivalents in South America and those in the Francevillian sequence (ca. 2.2-2.1 Ga), Gabon are correlatable to this period. Tectonically forced doming-up, attenuation and substantial increase in freeboard areas prompted increased silicate weathering and atmospheric CO₂ drawdown causing glaciation on the Neoproterozoic Rodinia supercontinent. Tectonic rifting and mantle outgassing led to deglaciation. Dissolved Mn²⁺ and Fe²⁺ concentrated earlier in highly saline stagnant seawater below the ice cover were exported to shallow shelves by transgression during deglaciation. During the Sturtian glacial-interglacial event (ca. 750-700 Ma), interstratified Mn oxide and BIF deposits of Damara sequence, Namibia, was formed. The Varangian (≡ Marinoan; ca. 600 Ma) cryogenic event produced Mn oxide and BIF deposits at Urucum, Jacadigo Group, Brazil. The Datangpo interglacial sequence, South China (Liantuo-Nantuo ≡ Varangian event) contains black shale-hosted Mn carbonate deposits. The Early Paleozoic witnessed several glacioeustatic sea level changes producing small Mn carbonate deposits of Tiantaishan (Early Cambrian) and Taojiang (Mid-Ordovician) in black shale sequences, China, and the major Mn oxide-carbonate deposits of Karadzhal-type, Central Kazakhstan (Late Devonian). The Mesozoic period of intense plate movements and volcanism produced greenhouse climate and stratified oceans. During the Early Jurassic OAE, organic-rich sediments host many Mn carbonate deposits in Europe (e.g., Úrkút, Hungary) in black shale sequences. The Late Jurassic giant Mn Carbonate deposit at Molango, Mexico, was also genetically related to sea level change. Mn carbonates were always derived from Mn oxyhydroxides during early diagenesis. Large Mn oxide deposits of Cretaceous age at Groote Eylandt, Australia and Imini-Tasdremt, Morocco, were also formed during transgression-regression in greenhouse climate. The Early Oligocene giant Mn oxide-carbonate deposit of Chiatura (Georgia) and Nikopol (Ukraine) were developed in a similar situation. Thereafter, manganese sedimentation was entirely shifted to the deep seafloor and since ca. 15 Ma B.P. was climatically controlled (glaciation-deglaciation) assisted by oxygenated polar bottom currents (AABW, NADW). The changes in climate and the sea level were mainly tectonically forced.     

中太平洋海盆表层沉积物及其与锰结核的关系

通过对中太平洋海盆表层沉积物与相伴生的锰结核的研究表面,丰度、品位等有明显的差异,在深海粘土中锰结核干度最度,钙质软泥多,锰结核的发现聚集与沉积物类型,沉积速率、孔隙度、金属含量及形成时的氧化还原条件,水深、底层流等的影响.锰结核的形成,发育与富集是受多种因素所控制,是一个模式内的约制。     

Biostratigraphy and depositional environments of subsurface sediments in well Arani-A,Palar basin,Tamil Nadu

The first exploratory well Arani–A was drilled in the Palar basin to a depth of 2400m and terminated within the granitic basement.This well offered the first ever opportunity to understand biostratigraphy, sedimentation history and depositional environment of the entire sedimentary column based on arenaceous foraminifera, spores, pollen and dinoflagellate cyst assemblages. Previous studies on few scattered outcrops around Sriperumbudur, Chengalpattu and Sathyavedu areas have documented palynofossil assemblage of Neocomian–Aptian age. The present study reveals the presence of middle Jurassic (Bajocian-Callovian) sediments (2360-1725 m) resting on the granitic basement. The sediments are interpreted to have deposited under lacustrine/estuarine conditions with high tides providing occasional marine influence. The middle Jurassic sediments are conformably overlain by late Jurassic (Oxfordian–Tithonian) sediments (1725 - 950 m). The late Jurassic sediments have been inferred to have got deposited under fluctuating near shoremarginal marine conditions. There is a 55m thick boulder bed (950 - 895 m) separating the overlying Valanginian sediments. Early Cretaceous (Valanginian-Early Albian) sediments are developed in the interval from 895-50m. The boulder bed possibly corresponds to the missing Berriasian stage of the earliest Cretaceous representing an unconformity of the order of ~5 Ma across Jurassic-Cretaceous boundary. These sediments are inferred to have deposited under shallow inner neritic conditions. The sediments from 50m to surface consist mainly of lateritic sandstone and alluvium. The sedimentary history of Palar basin began in Bajocian stage of middle Jurassic (170-168 Ma) and ended in early Albian stage of early Cretaceous (113-105 Ma). The late Albian marine transgression which facilitated huge sedimentation in Cauvery and Krishna-Godavari basins has bypassed the Palar basin thus adversely affecting the hydrocarbon potential.     

Sedimentation rates, basin analysis and regional correlations of three Neoarchaean and Palaeoproterozoic sub-basins of the Kaapvaal craton as inferred from precise U–Pb zircon ages from volcaniclastic sediments

Calculation of sedimentation rates of Neoarchaean and Palaeoproterozoic siliciclastic and chemical sediments covering the Kaapvaal craton imply sedimentation rates comparable to their modern facies equivalents. Zircons from tuff beds in carbonate facies of the Campbellrand Subgroup in the Ghaap Plateau region of the Griqualand West basin, Transvaal Supergroup, South Africa were dated using the Perth Consortium Sensitive High Resolution Ion Microprobe II (SHRIMP II). Dates of Ma and Ma for the middle and the upper part of the Nauga Formation indicate that the decompacted sedimentation rate for the peritidal flat to subtidal below-wave-base Stratifera and clastic carbonate facies, southwest of the Ghaap Plateau at Prieska, was of up to 10 m/Ma, when not corrected for times of erosion and non-deposition. Dates of Ma for the upper Gamohaan Formation and for the upper Monteville Formation, indicate that some 2000 m of carbonate and subordinate shale sedimentation occurred during 16 Ma to 62 Ma on the Ghaap Plateau. For these predominantly peritidal stromatolitic carbonates, decompacted sedimentation rates were of 40 m/Ma to over 150 m/Ma (Bubnoff units). The mixed siliciclastic and carbonate shelf facies of the Schmidtsdrif Subgroup and Monteville Formation accumulated with decompacted sedimentation rates of around 20 B. For the Kuruman Banded Iron Formation a decompacted sedimentation rate of up to 60 B can be calculated. Thus, for the entire examined deep shelf to tidal facies range, Archaean and Phanerozoic chemical and clastic sedimentation rates are comparable. Four major transgressive phases over the Kaapvaal craton, followed by shallowing-upward sedimentation, can be recognized in the Prieska and Ghaap Plateau sub-basins, in Griqualand West, and partly also in the Transvaal basin, and are attributed to second-order cycles of crustal evolution. First-order cycles of duration longer than 50 Ma can also be identified. The calculated sedimentation rates reflect the rate of subsidence of a rift-related basin and can be ascribed to tectonic and thermal subsidence. Comparison of the calculated sedimentation rates to published data from other Archaean and Proterozoic basins allows discussion of general Precambrian basin development. Siliciclastic and carbonate sedimentation rates of Archaean and Palaeoproterozoic basins equivalent to those of younger systems suggest that similar mechanical, chemical and biological processes were active in the Precambrian as found for the Phanerozoic. Particularly for stromatolitic carbonates, matching modern and Neoarchaean sedimentation rates are interpreted as a strong hint of a similar evolutionary stage of stromatolite-building microbiota. The new data also allow for improved regional correlations across the Griqualand West basin and with the Malmani Subgroup carbonates in the Transvaal basin. The Nauga Formation carbonates in the southwest of the Griqualand West basin are significantly older than the Gamohaan Formation in the Ghaap Plateau region of this basin, but are in part, correlatives of the Oaktree Formation in the Transvaal and of parts of the Monteville Formation on the Ghaap Plateau.     

广西德保县荣华锰矿床地质特征研究

荣华锰矿赋存于桂西三叠系百逢组中,为该层位首次发现的中型规模锰矿。笔者通过参与矿区锰矿勘查工作,采用室内外观测、测试、工程揭露和验证等手段,对研究区地层、构造、沉积演化、含矿层位、矿体及矿石矿物特征、矿床成因和找矿标志等方面进行了分析探讨。研究发现荣华锰矿为典型的沉积-锰帽型矿床,严格受地层和构造因素控制;矿石类型主要为氧化锰矿贫锰矿石;氧化锰矿物主要为水羟锰矿、硬锰矿及软锰矿;矿床成因与原始沉积作用、后期风化淋滤等有重要关系;百逢组浊积岩之下、罗楼组碳酸盐岩之上的狭窄范围是荣华锰矿的典型找矿标志,该标志对大量出露三叠系百逢组的桂西地区具有普遍意义,同时指出桂西地区该组地层内具有良好的找矿前景。     

Unstable Climate Oscillations during the Late Holocene in the Eastern Bransfield Basin, Antarctic Peninsula

Core A9-EB2 from the eastern Bransfield Basin, Antarctic Peninsula, consists of pelagic (diatom ooze-clay couplets and bioturbated diatom ooze) and hemipelagic (bioturbated mud) sediments interbedded with turbidites (homogeneous mud and silt–clay couplets). The cyclic and laminated nature of these pelagic sediments represents alternation between the deposition of diatom-rich biogenic sediments and of terrigenous sediments. Sediment properties and geochemical data explain the contrasting lamination, with light layers being finer-grained and relatively rich in total organic carbon and biogenic silica content. Also, the high-resolution magnetic susceptibility (MS) variations highlight distinct features: high MS values coincide with clastic-rich sections and low MS values correspond to biogenic sections. The chronology developed for core A9-EB2 accounts for anomalous ages associated with turbidites and shows a linear sedimentation rate of approximately 87 cm/10³ yr, which is supported by an accumulation rate of 80 cm/10³ yr calculated from ²¹⁰Pb activity. The late Holocene records clearly identify Neoglacial events of the Little Ice Age (LIA) and Medieval Warm Period (MWP). Other unexplained climatic events comparable in duration and amplitude to the LIA and MWP events also appear in the MS record, suggesting intrinsically unstable climatic conditions during the late Holocene in the Bransfield Basin of Antarctic Peninsula.     

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。     

Origin of authigenic carbonates in sediment from the deep Bering Sea

Forty beds of authigenic carbonate were identified from the deep Bering Sea in cores taken on Leg 19 of the Deep Sea Drilling Project. Carbonate minerals were mainly high-magnesium calcite and protodolomite, less commonly siderite, rhodo-chrosite, low-magnesium calcite, and manganosiderite. Authigenic carbonates cement and replace diatom ooze, ash and bentonite beds, and, less commonly, clastic beds. Replacement zones are as much as 60 cm thick. Eighty-five per cent of carbonate beds occurred below 400 m sub-bottom depth and 70% in sediment older than 4 m.y. δ¹³C values averaged -17.20^0/00 PDB and δ¹⁸O ranged from 18.59 to 34–11^0/00SMOW. The carbon was derived from oxidation of organic matter under anaerobic conditions during bacterial reduction of sulphate, or from CO₂ produced in concert with CH₄ during degradation of organic matter. The cations (Ca, Mg, Fe, Mn) were derived from alteration of ash beds. In Bering Sea deposits, ash beds altered to smectite within about 3–5 m.y. Carbonate precipitated simultaneously at different stratigraphic levels within the 627–1057 m sections at temperatures of 7–85°C. No apparent calcite precursor of biogenic origin was found for these authigenic carbonates.     

Genesis of carbonates from the Parnok ferromanganese deposit,Polar Urals

The Parnok deposit is made up of stratiform lodes of iron (magnetite) and manganese (oxide-carbonate, carbonate, and carbonate-silicate) ores localized among terrigenous-carbonate sediments (black shales) on the western slope of the Polar Urals. The lithological study showed that ore-bearing sediments were accumulated in a calm hydrodynamic setting within a relatively closed seafloor area (trap depressions). Periodic development of anaerobic conditions in the near-bottom seawater was favorable for the accumulation of dispersed organic matter in the terrigenous-carbonate sediments. Carbon required to form calcium carbonates in the ore-bearing sediments was derived from carbon dioxide dissolved in seawater. In the organic-rich sediments, carbonates were formed with the participation of carbon dioxide released by the destruction of organic matter. However, δ¹³C values (from 0.5 to ?4.4‰ PDB) suggest a relatively low fraction of the isotopically light biogenic carbon in the host calcite. The most probable sources of Fe and Mn were hydrothermal seepages at the seafloor. The Eh-pH conditions during stagnation were favorable for the precipitation of Fe and accumulation of Mn in a dissolved state. Transition from the stagnation regime to the concentration of oxygen in near-bottom waters was accompanied by oxidation of the dissolved Mn and its precipitation. Thus, fluctuations in Eh-pH parameters of water led to the differentiation of Fe and Mn. Initially, these elements were likely precipitated as oxides and hydroxides. During the subsequent lithification, Fe and Mn were reduced to form magnetite and rhodochrosite. The texture and structure of rhodochrosite aggregates indicate that manganese carbonates already began to form at the diagenetic stage and were recrystallized during the subsequent lithogenetic stages. Isotope data (δ¹³C from ?8.9 to ?17.1‰ PDB) definitely indicate that the oxidized organic matter of sediment served as the main source of carbon dioxide required to form manganese carbonates. Carbonates from host rocks and manganese ores have principally different carbon isotopic compositions. Unlike carbonates of host rocks, manganese carbonates were formed with an active participation of biogeochemical processes. Further processes of metagenesis (T ≈ 250–300°C, P ≈ 2 kbar) resulted in the transformation of textures, structures, and mineral composition of all rocks of the deposit. In particular, increase in temperature and pressure provided the formation of numerous silicates in manganese ores.     

Structure and Composition of Ferromanganese–Phosphate Nodules from the Black Sea

Ferruginate shells and tubular worm burrows from the oxygenated zone of the Black Sea (Kalamit Bay and Danube River mouth) are studied using transmission and scanning electron microscopy combined with analyses of elemental composition. Iron and manganese hydroxide nodules considered here are enriched in phosphorus. They contain variable amounts of terrigenous and biogenic material derived from host sediments. The hydroxides are mainly characterized by colloform structure, whereas globular and crystalline structures are less common. The dominating iron phase is represented by ferroxyhite and protoferroxyhite, whereas the manganese phase is composed of Fe-free vernadite. Relative to sediments, concentrations of Mn, As, and Mo increase 12–18 times, while concentrations of Fe, P, Ni, and Co increase 5–7 times during the nodule formation.