Formation of nano-crystalline todorokite from biogenic Mn oxides

Todorokite, as one of three main Mn oxide phases present in oceanic Mn nodules and an active MnO₆ octahedral molecular sieve (OMS), has garnered much interest; however, its formation pathway in natural systems is not fully understood. Todorokite is widely considered to form from layer structured Mn oxides with hexagonal symmetry, such as vernadite (δ-MnO₂), which are generally of biogenic origin. However, this geochemical process has not been documented in the environment or demonstrated in the laboratory, except for precursor phases with triclinic symmetry. Here we report on the formation of a nanoscale, todorokite-like phase from biogenic Mn oxides produced by the freshwater bacterium Pseudomonas putida strain GB-1. At long- and short-range structural scales biogenic Mn oxides were transformed to a todorokite-like phase at atmospheric pressure through refluxing. Topotactic transformation was observed during the transformation. Furthermore, the todorokite-like phases formed via refluxing had thin layers along the c^∗ axis and a lack of c^∗ periodicity, making the basal plane undetectable with X-ray diffraction reflection. The proposed pathway of the todorokite-like phase formation is proposed as: hexagonal biogenic Mn oxide → 10-Å triclinic phyllomanganate → todorokite. These observations provide evidence supporting the possible bio-related origin of natural todorokites and provide important clues for understanding the transformation of biogenic Mn oxides to other Mn oxides in the environment. Additionally this method may be a viable biosynthesis route for porous, nano-crystalline OMS materials for use in practical applications.     

Early Cretaceous araucarian driftwood from hemipelagic sediments of the Puez area,South Tyrol,Italy

We describe a calcareously permineralised fossil tree-trunk, preserved as driftwood, within hemipelagic sediments of the Cretaceous Puez Formation near Wolkenstein, South Tyrol, Italy. Planktic foraminiferal assemblages recovered from the marls containing the fossil wood indicate a latest middle Albian age. Based on its wood anatomy, the trunk is assigned to Agathoxylon and probably has an affinity with the conifer family Araucariaceae. The wood lacks pronounced tree-rings consistent with tree growth within the broad humid tropical belt that existed at that time. The trunk contains cylindrical chambers filled within faecal pellets, demonstrating that oribatid mites infested the tree, either during life, or shortly after death. Prior to final burial, the tree-trunk drifted out into the open sea for a considerable period as indicated by extensive borings assigned to the ichnospecies Teredolites longissimus and produced by teredinid bivalves. Relatively little is known about the Cretaceous floras of Italy, so this new finding fills a gap in our knowledge of the composition and ecology of the vegetation of this region.     

The influence of humic substances on the geochemistry of iodine in nearshore and hemipelagic marine sediments

Iodine is characteristically enriched at the surface of hemipelagic and nearshore sediments deposited under oxygenated conditions. In such sediments, bulk I/C_org ratios usually decrease with depth to values which are characteristic of anoxic sediments, reflecting a preferential release of I during early diagenesis. There is some debate as to whether sedimentary I is associated with the iron oxyhydroxide phase or with the organic fraction, and whether the decrease in I/C_org with depth is due to the dissolution of the iron oxyhydroxides or the decomposition of labile organic matter.It is shown that in a surficial hemipelagic sediment sample and in a nearshore sediment core I is mainly associated with the organic fraction and, moreover, that humic substances are involved in the surficial iodine enrichment. Laboratory experiments on the uptake and release of I by and from sedimentary humic substances also suggest a mechanism whereby humic materials reduce iodate at the sediment/water interface to an electrophilic I species which further reacts with the organic matter to produce iodinated organic molecules. During burial, this excess I could be displaced from the organic matrix by nucleophiles such as sulphide ions or thiosulphate, thus providing a possible explanation for the decrease in I/C_org ratio with depth observed in many nearshore and hemipelagic sediments.     

Provenance and distribution of tethyan pelagic and hemipelagic siliceous sediments,pindos mountains,Greece

The broad range of time over which ribbon bedded cherts were deposited does not extend into the present marine environment, and no ribbon cherts have been recovered from the sea floor by the Deep Sea Drilling Project. The depositional environment of bedded cherts is difficult to determine, but extra-silicic impurities in the rock may offer clues about the provenance of the non-biogenic component. To test the usefulness of relative abundances of the extra silicic components in extracting information on the depositional environment of the chert, I analyzed the major element chemistry of chert samples from a broad range of environments including ophiolite-associated chert from the Franciscan Formation of California, deep-sea chert and porcellanite from the northwest Pacific (DSDP Leg 32), shallow pelagic shelf chert nodules from the Chalk of Britain, continental marginal basin chert from the Monterey Formation of California, and continental marginal basin chert from the Pindos Zone of Greece. The ratios FeO/A1₂O₃, TiO₂/A1₂O₃ and A1/A1+Fe+Mn were considered in detail. The interpretative logic is simple but empirically supported by observations of these ratio values at different depositional environments in the Pacific: A1 is concentrated most highly in continental material while Fe and Mn are more concentrated in pelagic sediments. FeO/A1₂O₃ can be used to differentiate between ophiolite associated chert and chert associated only with other sediments. TiO₂/A1₂O₃ is not a useful indicator, possibly because of the equalizing effect of widespread eolian transport. The A1/A1+Fe+Mn ratio was measured in detail in one stratigraphic section in central continental Greece. This ratio varied with the type of sediment admixture, decreasing in value after the influx of ophiolite debris-bearing sediments, even when their presence was undetectable in hand sample or under petrographic microscope.To help clarify the paleogeography of the main study area, the Pindos Zone, and to identify sources and dispersal patterns of extra-basinal materials, isopach maps of sedimentary facies of the Pindos were constructed. Superimposed directly upon the series of imbricated thrust slices that comprise the Pindos Zone, the maps are at best compressed pictures of the Pindos Sea Floor. Persistent regional variation of facies thicknesses over time suggests the existence of several smaller depressions surrounded by submarine highs in the Pindos Basin.     

Use of clay fabric to distinguish turbidites from hemipelagic siltstone

In a recent paper O'Brien, Nakazawa & Tokuhashi (1980) summarized observations of clay fabric in some Pliocene and Holocene siltstones and silts. They demonstrated that clay fabric could be used, in combination with other sedimentary features, to distinguish hemipelagic sediments and turbidites.     

Terrigenous sand in Labrador Sea hemipelagic sediments and paleoglacial events on Baffin Island over the last 100,00 years

Eight Labrador Sea piston cores with faunal and ash-zone stratigraphies correlated to deep-sea oxygen isotope stages were used to compute Labrador Sea terrigenous sand input rates (mg/cm²/1000 years) during the last 100,000 years. Sources of the sand in Labrador Sea cores are likely to be ice-rafting, turbid glacial meltwater inflow or deflation and wind erosion of unvegetated landscapes in the wake of retreating continental ice sheets. High levels of sand input to the Labrador Sea are therefore undoubtedly glacier-related while low levels of sand input are not. Comparison of the history of Labrador Sea sand input with the chronology of glacial and non-glacial events on Baffin Island reveals that the era of highest sand input rates, the isotopic stage 5a/4 transition, closely coincided with an episode of early Foxe glacier advance to tidewater (Ayr Lake Stade) along the outer coast of Baffin Island ca. 80,000 B.P. to 60,000 B.P. The period of lowest Labrador Sea sand input rates, late isotopic stage 3 to the present, largely corresponds to a major disconformity in the raised marine and glacigenic sediments on Baffin Island, but includes also the late Foxe/early Holocene Cockburn glacial advance (which did not reach the outer coast of the island) and the modern glacial minimum. Labrador Sea and central-subpolar North Atlantic sand input histories are reciprocally related over the last 80,000 years. Accelerated sand input in the Labrador Sea during times of reduced sand input in the North Atlantic implies: (1) major early Wisconsin glacier expansion in the circum Labrador Sea/Baffin Bay region and/or; (2) a surface circulation pattern in the North Atlantic which inhibited iceberg melting there while delivering icebergs and relatively warm surface water into the Labrador Sea. Conversely, reduced sand input in the Labrador Sea during times of accelerated sand input in the North Atlantic implies: (1) late Wisconsin glacier recession in the circum Labrador Sea/Baffin Bay region and/or; (2) a circulation pattern which carries icebergs southward and eastward away from the Labrador Sea. These implications are discussed in the light of paleoceanographic evidence for three periods - 80,000 B.P. to 57,000 B.P.; 25,000 B.P. to 13,000 B.P.; and 13,000 B.P. to 9800 B.P     

The formation of todorokite and birnessite in sea water pumped from under ground

Manganese oxides precipitated from aerated well sea water at the Marine Science Museum, Tokai University, have been analyzed chemically and mineralogically. The $\text{O}\text{Mn}$ ratios are lower in todorokite than in birnessite but these minerals have similar contents of minor transition metals, which can be taken up additionally from sea water after the precipitation of Mn oxides. On the basis of these results, the genesis of Mn minerals is discussed in relation to marine Mn nodules.     

Formation of artifacts in sediments upon freeze-drying

Comparison of the analytical data on the alkenes extracted from both dried and wet Messel shale sediment points to the formation of artifacts, presumably as a result of clay-catalyzed dehydration reactions.     

Formation of vivianite in holocene clay sediments

Concretions of vivianite attaining 0.5 g occur in the upper 4 m of the bottom sediments of the Åsrum lake, Vestfold, S. Norway. The vivianite-bearing zone is of lacustrine origin. Vivianite is absent in the underlying lagunal and marine sediments. Electro-chemical and chemical data are given for the interstitial water and the clay.

Solubility product of vivianite is determined. The equilibrium constant is K = 10⁻⁴⁰ for the reaction 3 Fe⁺⁺ + 2 HPO₄⁻ + 2 OH⁻ = vivianite. The concretions grew by diffusion from a slightly supersaturated interstitial water phase. The degree of supersaturation is calculated. The stability relations of vivianite and hydroxyl apatite are discussed.     

Diagenesis of metal-organic complexes in sediments: Formation of metal sulphides from cystine complexes

Metal-cystine complexes of iron, lead, zinc, copper and nickel under mild artificial diagenesis give rise to crystalline metal sulphides and insoluble organic matter as well as gaseous and “oily” organic products. Under confined reducing conditions at 200°C for 100 h a virtual 100% conversion of metal complex to metal sulphide occurs, while < 10% of the associated organic material may remain as kerogen. Such a mechanism could account for the formation of metal sulphides and in particular pyrite from protein- or amino acid-rich material in carbonaceous sediments during diagenesis.     

Late Maastrichtian litho- and ecocycles from hemipelagic deposits of eastern Sinai, Egypt

A biostratigraphical and palaeoecological survey employing calcareous nannofossils and planktonic and benthonic foraminifera has been carried out in four sections of hemipelagic marls and chalks of the Late Maastrichtian Abathomphalus mayaroensis Zone of eastern Sinai, in order to evaluate the mechanisms controlling the composition of the well preserved microfauna and nannoflora.The Abathomphalus mayaroensis Zone in eastern Sinai can be easily identified by the wide occurrence of the index fossil A. mayaroensis and can be further subdivided by the first occurrences of Plummerita reicheli (ex. P. hantkeninoides) and Micula prinsii. Microfossil abundances and lithologies are characterised by pronounced repetitive distribution patterns. These include low and high frequency fluctuations of the planktonic/benthonic (P/B) foraminiferal ratio, repetitive changes in the abundance of calcareous nannofossils and benthonic foraminifera, as well as the development of chalk-marl couplets and thinning upward chalk packets. both microfossil distribution patterns and the occurrence of rhythmites are attributed to changes in primary palaeoproductivity. Semiquantitative investigations of calcareous nannofossils and a few selected benthonic foraminifera yield evidence of the presence of high (HP) and low (LP) productivity assemblages.The interpreted HP assemblage is dominated by Glaukolithus diplogrammus, Manvitella pemmatoidea, Microrhabdulus decoratus and Micula murus and the benthonic foraminifera Neoflabellina jarvisi; the LP assemblage is characterised by Lithraphidites quadratus and Bolivinoides draco. However, further quantitative studies are necessary to reconstruct the exact composition of these assemblages and to explain deviatory developments. The chalk-marl couplets, thinning-upward chalk packets and the high frequency P/B patterns are interpreted to reflect productivity changes related to orbital forcing. These hemipelagites were deposited during the latest phase of the southern Tethyan upwelling system, which was active from the Santonian to the Late Maastrichtian with a peak in the Campanian. Termination of upwelling just before the K/T boundary also provides a good explanation for the change towards a palaeobathymetric control on foraminiferal distribution, as observed for the Palaeocene of central east Sinai.     

Formation of authigenic clays in Mesozoic sediments of Fergana Depression

The humid-acid and arid-alkaline conditions of sedimentation, Jurassic and Cretaceous respectively, have recognizable expressions in associations of clay minerals (fig. 2), which by comprehensive analyses, comparisons, and other studies and identifications, type-by-type and stage-by-stage, prove to be authigenic. Prevalence of kaolin or montmorillonite (with palygorskite) are expressions of the humid-acid and arid-alkaline environments of the authigenes. There seems no definite relationship of the kind for authigenic hydromicas.     

Formation and reactions of alkyl adamantanes in sediments: Carbon surface reactions

Diamondoids are hydrocarbons with a carbon skeleton that is superimposable on the diamond lattice. Adamantane is the cage-shaped primary unit of diamondoids and occurs widely in sediments and petroleum. The first report of adamantane isolated from petroleum extends back seven decades, but the precursors and reaction mechanisms for the formation of adamantane and related diamondoids in sediments has remained unclear. We report the formation of alkyl adamantanes by heating β-ionone with activated carbon in closed system pyrolysis experiments in the range 170-320 °C. In addition, hydrogen exchange, demethylation, methyl transfer and isomerisation reactions were observed when the model compounds adamantane and 1,3-dimethyladamantane were heated at moderate temperature with activated carbon. A reaction pathway for the formation and reactions of alkyl adamantanes is proposed on the basis of ring isomerisation of adamantane to protoadamantane on the activated carbon surface. The carbonaceous surface reactions described help account for the occurrence and distribution of alkyl adamantanes in petroleum basins, as evidenced by the strong linear relationships between compound pairs related by isomerisation and demethylation for a set of crude oils from the Carnarvon Basin, Western Australia.     

青海省贵南县过马营一带早中三叠世隆务河组沉积特征

青海贵南县过马营一带隆务河组为一套典型的浊流沉积,对此套浊积岩的沉积特征进行研究。通过对过马营一带隆务河组浊积岩的岩石组合特征、地层层序及鲍玛层序特征分析,探讨其沉积环境特征,并与典型浊积扇模式对比,建立沉积模型。综合分析认为,隆务河组由下向上的3个段分别位于浊积扇的外扇、中扇、内扇,其中中扇辫状河道发育。此研究对于西秦岭造山带的沉积环境分析及构造演化具有重要的意义。     

准噶尔盆地车莫古隆起内物源沉积体系探讨及勘探意义——以白垩系清水河组一段为例

为了探讨车莫古隆起对内物源沉积体系及油气成藏的控制作用,从车莫古隆起形成与演化入手,利用岩心、地震、测井等资料,多种方法结合恢复其剥蚀量、古地貌,提出车莫古隆起从中侏罗世到早白垩世发育,侏罗世末是其鼎盛时期,并提供内物源,控制围绕车莫古隆起周缘沉积体系和砂体展布,从岩心、地震特征、重矿物稳定系数、古水流指向、砂岩厚度等方面给出存在依据,合理解释了古隆起控制范围内已发现油藏的砂体成因。车莫古隆起发育和潜伏埋藏期控制古油气藏的形成与分布,掀斜后内物源砂体展布、断裂体系和现今构造共同控制着油气调整、运移及次生油气藏的分布,围绕车莫古隆起发育的内物源砂体尖灭方向与现今构造高部位指向垂直和斜交区域是岩性地层油气藏有利区。围绕内物源勘探刚开始,在此认识指导下部署的沙门1、莫17、夏盐11、夏盐12等井已获得突破,腹部岩性地层油气藏勘探将进入一个油气发现新阶段。     

鄂尔多斯盆地二叠系山西组及下石盒子组盒8段南北物源沉积汇水区与古地理

在对鄂尔多斯盆地目的层段总体资料了解的基础上,对盆地南部4个露头剖面、18口井岩心的砂岩进行了切片分析,根据长石含量变化和其他岩矿特征、测井曲线与岩石组合特征、连井剖面以及露头沉积相分析,明确了山西组-下石盒子组盒8段沉积物在盆地南部的汇水区位置。“汇水区”指搬运南北物源沉积物的流水汇聚区,它大体上是南北物源沉积物分布的分界区、大致呈东西向分布。汇水区南北的长石含量存在明显差异。提出了在汇水区局部又存在南北物源沉积“交互区”的认识,“交互区”指南北物源沉积物抵达汇水区并在局部地段发生交互的地区,它是南北物源沉积物的连通区。交互区位于汇水区并分隔汇水区。在盒8段交互区发现了还原条件下形成的早期成岩矿物——菱铁矿结核。盆地南部山西期一盒8沉积期的沉积古地理受南部和北部物源沉积物的双重影响,连井剖面显示汇水区南北沉积相带具有对称分布的特征,其沉积单元和相带包括：（1）汇水区,含3个交互区;（2）汇水区南缘三角洲相带,含来自南部物源的3个三角洲;（3）汇水区北缘三角洲相带。含来自北部物源的4～5个三角洲;（4）与南、北三角洲相带过渡的河流相带。在上述认识的基础上,绘制了研究区目的层段沉积模式图。     

The use of microstructures for discriminating turbiditic and hemipelagic muds and mudstones

The microstructures of turbiditic and hemipelagic muds and mudstones were investigated using a scanning electron microscope to determine whether there are microstructural features that can differentiate turbiditic from hemipelagic sedimentary processes. Both types of muddy deposits are, in general, characterized by randomly‐oriented clay particles. However, turbiditic muds and mudstones also characteristically contain aggregates of ‘edge‐to‐face’ contacts between clay particles with long‐axis lengths of up to 30 μm. Based on observations of the clay fabric of the experimentally‐formed muds settled from previously agitated muddy fluids, these types of aggregates, hereafter referred to as ‘aggregates of clay particles’, are interpreted as having been formed by the collision of component flocs in turbulent fluids. Furthermore, some aggregates of clay particles have ‘face‐to‐face’ contacts between clay particles; this is similar to face‐to‐face aggregates characteristically developed in fluid‐mud deposits that are commonly recognized only in turbiditic mudstones, indicating the possibility of a final stage of deposition under highly‐dense conditions, such as temporary fluid muds. In conjunction with earlier proposed lithofacies‐based and ichnofacies‐based criteria, aggregates of clay particles should be useful for the differentiation of turbiditic and hemipelagic muddy deposits, particularly with limited volumes of non‐oriented samples from deep‐water successions.     

Use of clay fabric to distinguish turbiditic and hemipelagic siltstones and silts

Pliocene and Holocene siltstones and silts in outcrops from the Boso Peninsula, Japan and in cores from the East China were studied to determine distinctive characteristics of the turbiditic (Bouma E-Division) and hemipelagic siltstones and silts. Weathering characteristics, colour, grain size, and organic carbon-organic nitrogen ratio, plus clay fabric proved valuable in characterizing each unit. Clay and non-clay mineral content was uniform throughout. Clay fabric differences are pronounced. Random clay flake orientation prevails in the turbiditic interval while the hemipelagic unit has more preferred orientation. The fabric reflects different conditions of sedimentation. The turbiditic clay was deposited more rapidly in the flocculated state while the interturbidite hemipelagic clay may have formed from more slowly sedimented dominantly dispersed clay. Results suggest that clay fabric may be useful in combination with other sedimentary features in the study of mud-turbidite sedimentation.     

Formation of pyrite in freshwater sediments: Implications for C/S ratios

The vertical distribution of pyrite, acid volatile sulphide (AVS), carbon, and total S (St) were determined directly in the sediments of three lakes of different trophic status. The results showed that freshwater pyrite formation reflects the redox status of the sediment or overlying waters. It appears to form chiefly in reducing sediments which are subject to oxidizing influences, by either a low turnover of organic carbon or periodic incursions of oxygen. Although there are high concentrations of AVS in the near-surface sediments of productive lakes, very little is diagenetically converted to pyrite.The feasibility of using sulphur ratios to diagnose whether rocks were formed in marine or freshwater environments is assessed. New values for FeS₂/FeS of 0.5-5 show that this ratio does not provide a reliable test. Values of C/Sp, where Sp represents pyrite sulphur, lie within the range of 160–700 and are much higher than previously measured ratios of C/S_t of 1–50. These new determinations show that, if pyrite sulphur is unequivocally measured, C/S ratios may be a more sensitive indicator of salinity than had been previously thought.     

Formation mechanisms of illite,chlorite and mixed-layer illite-chlorite in Triassic volcanogenic sediments from the Southland Syncline,New Zealand

Clay minerals from the three principal kinds of zeolitic sediments from the type area for zeolite facies alteration, the Triassic Murihiku Supergroup, Southland, New Zealand, have been studied by TEM. Bentonitic tuff consists largely of smectite and heulandite with minor illite; they occur as replacements of glass shards and are inferred to be direct alteration products of tuff alteration. Both analcime- and laumontite-rich tuffs contain chlorite, illite and mixed-layer illite-chlorite, including 11 mixed-layer sequences. Subhedral to euhedral phyllosilicate crystal shapes and other textural features imply that phyllosilicates crystallized from solution derived in part by dissolution of precursor smectite. Intralayer transitions involving illite and chlorite are inferred to be products of crystallization rather than direct alteration and replacement. Petrographically similar bentonitic and analcimized tuffs overlap each other in the stratigraphic section, supporting earlier observations that there is no systematic change in smectite relative to the illite plus chlorite derived from smectite in sections up to 8.5 km thick. The data imply that smectite may be metastable relative to illite plus chlorite. Permeability and fluid chemistry are inferred to be as significant as temperature in promoting reactions in clay minerals as well as zeolites during burial metamorphism.Contribution No. 436, from The Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan 48109