The diagenetic history of some septarian concretions from the Kimmeridge Clay, England

ABSTRACT
Large septarian concretions from the Kimmeridge Clay, up to 1.2 m in diameter, have centres comprising anhedral calcite microspar passing into margins of radiating fibrous calcite microspar, with a pyrite-rich zone at the transition. Septarian veins formed and were lined with brown calcite synchronously with fibrous matrix growth, with white calcite precipitated in septarian cavities after concretion growth ceased. Septarian veins, filled only with white calcite, formed later, at the same time as the outermost calcite microspar crystals were enlarged.
The concretions were buried in the Late Jurassic to about 130 m, and in the Late Cretaceous to about 550 m, with uplift between. Oxygen isotopes show that the concretion grew throughout the first burial, with septarian veins forming from about 30 m depth onwards. Later septarian veins formed between about 200 and 500 m during the second burial.
Carbon isotopes show that the compact inner matrix grew in the sulphate reduction zone, the end of which is marked by the pyrite-enriched zone. Dissolving shells, and possibly minor methanogenic carbonate, slowly diluted sulphate reduction-zone carbonate during deeper burial. During early concretion growth, Mg and Sr were depleted in the pore water. During later stages of the first burial, Mg, Sr, Mn and Fe all increased, especially after concretion growth ceased. During the second burial, Fe, Mn and Mg decreased as calcite precipitated, implying relatively closed systems for these elements.
Synchronous formation of septarian fractures and fibrous calcite matrix shows that the Kimmeridge Clay became overpressured during the later stages of both burials.     

Petrography and geochemistry of septarian carbonate concretions from the Boom Clay Formation (Oligocene,Belgium)

The septarian carbonate concretions from the Boom Clay (Belgium) consist mainly of authigenic minerals such as micrite ( 70% bulk volume) and pyrite framboids ( 3%). These mineral phases occur between detrital grains and fossils. The septarian cracks are lined with calcite, which is sometimes covered with pyrite. The preservation of delicate sedimentological features in the concretion matrix (hardly compacted faecal pellets, burrows and uncrushed shells) points to an early origin of the concretions. Systematic geochemical variations from concretion centre to edge suggest that growth continued during shallow burial. The13C values (–17.5 to –20.5) of the concretionary carbonate show that bacterial sulphate-reduction processes were dominant. Sulphate-reduction-derived HCO3- was diluted by marine-related HCO3-, derived from dissolved bioclasts. A slight enrichment in 13C during growth is caused by the decreasing influence of sulphate reduction because of the progressive closure of the diagenetic system due to shallow-burial compaction. The 18O values (–0.5 to +1.0) of the concretionary carbonate point to a marine origin. The slightly 18O-depleted signature with respect to time-equivalent marine-derived carbonate relates to the incorporation of an 18O-depleted component, originating from sulphate and organic matter. The slight decrease in 18O during growth relates to an increasing influence of this component and to a decreasing influence of seawater-derived oxygen during early diagenesis.     

A new peculiar muensterellid coleoid (Cephalopoda) from the Kimmeridge Clay Formation of Dorset (England)

A concretion from the lower Tithonian Kimmeridge Clay Formation (Pectinatus Zone) found by Steve Etches yielded a gladius of a coleoid cephalopod. It is peculiar in shape and has an unusual ornamentation of radiating ribs and tubercles. The new form is named Etchesia martilli n. gen. n. sp. and preliminarily placed within the octobrachian family Muensterellidae based on its limpet-like gladius. Through the presence of radiating ribs as well as the absence of a narrow anterior rachis E. martilli n. gen. n. sp. is similar to Pearceiteuthis buyi from the Oxford Clay Formation (Callovian). The new muensterellid is unique in having an enrolled patella apex, which is located close to the posterior gladius rim. E. martilli n. gen. n. sp. represents the first muensterellid coleoid from the Kimmeridge Clay Formation. A phylogenetic relationship of E. martilli n. gen. n. sp. (and Pearceiteuthis) with cirrate and incirrate octopods is discussed, although further information on soft parts such as the muscular mantle is necessary.     

The concretions of the Bearreraig Sandstone Formation: geometry and geochemistry

The sandbodies of the Bearreraig Sandstone Formation (Inner Hebrides, UK) are cemented by two generations of calcite. The first generation, an inhomogeneous ferroan calcite (0.05?3.28 mol% FeCo₃) formed during sulphate reduction (δ¹³C =?24 to ?32%o PDB) in marine porewaters (δ¹⁸O of cement from ?1 to ?4%o PDB) at very shallow burial depths (a few centimetres). These cements are rare but form millimetre-scale clusters of crystals which acted as nuclei to the later, concretionary cements. The second generation of cements are more homogeneous ferroan calcites (mean 1?58% mol% FeCo₃) which evolve to progressively higher Fe/Mg ratios. They are sourced by shell dissolution (δ¹³C of cement from +1 to ?3%o PDB) into meteoric (δ¹⁸O of cement from ?6 to ?10%o PDB) or mixed marine meteoric waters (δ¹⁸O of cement from ?4 to ?6%o SMOW). These were introduced into the formation either during Bathonian times as a freshwater lens, or, subsequent to partial inversion, by confined aquifer flow. Corroded feldspars within the concretions suggest that an interval of at least 8 Ma separated the deposition of the sediments from the onset of concretion growth. Abundant concretions are preferentially developed at certain horizons within the sandbodies, where the early generation of ferroan calcite cements provided nuclei. The latter formed close to the sediment-water interface, the concentration of cement within the sediment being related to sedimentation rate. The relatively high concentrations of the first generation of cement, upon which the concretionary horizons are nucleated, formed during periods of minimal sedimentation.     

A truly gigantic pliosaur (Reptilia,Sauropterygia) from the Kimmeridge Clay Formation (Upper Jurassic,Kimmeridgian) of England

Four isolated cervical vertebrae from the Kimmeridge Clay Formation (Upper Jurassic, Kimmeridgian) of Abingdon, Oxfordshire, England are identified as from a pliosaurid plesiosaurian sauropterygian on account of their shortness relative to width and height, their near platycoelous nature and the location of tall rib facets on the centrum body. They are noteworthy for their size, with a maximum width of 269 mm, maximum height of 222 mm and maximum length of 103 mm. Simple scaling and comparisons with cervical vertebrae of Mid Jurassic pliosaurs Peloneustes and Liopleurodon, and the Early Cretaceous Stenorhynchosaurus and Sachicasaurus suggest a total body length of between ~ 9.8 m and 14.4 m for the Abingdon Kimmeridge Clay pliosaur. Likely the true length was towards the higher end of this range.A genus and species cannot be confidently determined on the basis of the described material, but they likely belong to Pliosaurus sp. or a similar animal, for which a precise neck length is not known. We estimate a neck length of 0.77 m for Pliosaurus ?brachyspondylus based on the average cervical lengths provided for specimen CAMSM J.35991.     

Early diagenetic carbonate precipitation and pore fluid migration in the Kimmeridge Clay of Dorset, England

In the argillaceous sequence of Kimmeridge Clay a carbonate rich bed is composed of ferroan dolomite cement with varying amounts of excess CaCO³, and Fe²⁺ substitution in the Mg²⁺ sites. The isotopic and chemical compositions change symmetrically about the centre of the band proving that it grew by vertical accretion during diagenesis. Textural and isotopic evidence shows that growth centred on a horizon rich in primary carbonate which became dolomitized and assimilated during production of diagenetic carbonate. This accounts for the lateral extent of the concretion. Early central diagenetic carbonate was produced from organic matter by bacterial fermentation (δ¹³C =+0.59‰) and later marginal carbonate by abiotic breakdown, (δ¹³C tending towards — 2.73‰). δ¹⁸O values range from — 1.56 to — 4.46‰ because the dolomite precipitated during progressive burial. As burial increased, magnesium, whose dominant source was trapped seawater, became depleted while the relative availability of Fe²⁺, whose source was dominantly reduced detrital oxides, increased. Dolomitization and the source of diagenetic components for dolomite formation are discussed. Diffusion and pore fluid migration transported ions to the site of precipitation. Early cementation of the band served to influence pore fluid migration, but thereafter pore fluid migration controlled carbonate precipitation.     

Growth mechanisms and geochemistry of carbonate concretions from the Cambrian Wheeler Formation (Utah,USA)

Carbonate concretions provide unique records of ancient biogeochemical processes in marine sediments. Typically, they form in organic‐rich mudstones, where a significant fraction of the bicarbonate required for carbonate precipitation is supplied from the decomposition of organic matter in the sediments. As a result, carbonates that comprise concretions are usually characterized by broad ranges in δ¹³C and include values that are significantly depleted relative to seawater. This article reports results from a physical, petrographic and geochemical analysis of 238 concretions from the Wheeler Formation (Cambrian Series 3), Utah, USA, which are unusual in several respects. Most prominently, they formed in organic‐poor mudstones (total organic carbon = 0·1 to 0·5%) and are characterized by a narrow range of δ¹³C that onlaps the range of contemporaneous seawater values. Subtle centre to edge trends in δ¹³C demonstrate that concretion precipitation was initiated by local chemical gradients set up by microbial activity in the sediments, but was sustained during growth by a large pool of inorganic bicarbonate probably derived from alkaline bottom waters. The large inorganic pool appears to have been important in facilitating rapid precipitation of the concretion matrix, which occurred via both displacive and replacive carbonate precipitation during early diagenesis. Stable isotope data from cogenetic pyrite (δ³⁴S) and silica (δ¹⁸O) phases provide insight into the evolution of biogeochemical processes during concretion growth, and suggest that concretions were formed almost entirely during sulphate reduction, with only minor modification thereafter. Concretions of the Wheeler Formation appear to represent an end‐member system of concretion formation in which rapid growth was promoted by ions supplied from sea‐water. As such, they offer insight into the spectrum of processes that may influence the growth of carbonate concretions in marine sediments.     

Major ion geochemistry of groundwaters from southern Nevada and eastern California, USA

The dissolved ionic constitutents of groundwaters are,in part,a recored of the minerals and rocks in aquifers through which the water has flowed.The chemical composition and association of these major ions in groundwaters have been used to trace groundwater flow paths and sources,In general,the chemical compostion of water in carbonate-rock aquifers in dominated by calcium,magnesium,and bicarbonate,whereas sodium,chloride,and sulfate can be dominant ions in the water that comes from volcanic aquifers or clay minerals.Since the 1990‘s,we have dealt with the geochemistry of groundwaters from more than 100 springs and wells in southern Nevada and eastrn california ,USA for major solutes and trace elements.This paper compiles the hydrochemical data of major ions of these groundwaters.Based on major ion geochemistry,groundwaters from southern Nevada and eastern California can be classified as carbonate aquifer water,volcanic aquifer water,and mixing water (either mixing of cabonate and volcanic aquifer waters or mixing with local recharges),Piper and stiff diagrams of major ions have graphically shown the general chemical characteristics,classification,and mixing relationships of groundwaters from southern Nevada and eastern California.     

Septarian concretions from the Oxford Clay (Jurassic, England, UK): involvement of original marine and multiple external pore fluids

Septarian concretions occur at several horizons within the Oxford Clay Formation, a marine mudstone containing pristine aragonite and immature biomarker molecules. They record the passage of at least four generations of pore fluids, the first of marine origin and the last still present in cavities. Concretion bodies formed, cracked, and calcite and pyrite precipitated in and around the cracks within the sulphate reduction zone, as demonstrated by C, O, S and Sr isotopic composition (Pore fluid 1). Before major compaction, sandstone dykes were intruded locally, and baryte precipitated, followed by coarse calcite cements with isotopically light oxygen and radiogenic strontium, indicating the introduction of meteoric-derived water (Pore fluid 2). Later, coarse celestine within concretions has distinct sulphur-isotopic composition and requires a further, geographically restricted, water source (Pore fluid 3). Celestine-bearing concretions contain water in tight cavities whose isotopic composition is close to that of modern precipitation. Its chemistry shows that it is equilibrating with pre-existing minerals implying a relatively recent origin (Pore fluid 4). The mineralogy of the Oxford Clay concretions shows that complex results can follow from a simple burial and uplift history, and that multiple generations of pore fluids can pass through a low-permeability clay.     

Leptolepid otoliths from the Hauterivian (Lower Cretaceous) Lower Weald Clay (southern England)

Teleostean saccular otoliths from the upper part of the late Hauterivian Lower Weald Clay Formation of the Wealden Supergroup exposed at Langhurstwood Quarry, West Sussex, UK, and Clockhouse Brickworks, Surrey, UK are described for the first time. Two new species of the genus Leptolepis, Leptolepis wealdensis and Leptolepis toyei are described. Many of the specimens are densely packed on individual bedding planes and they are interpreted as coprocoenotic accumulations. Additional mechanisms of deposition and concentration are discussed, in particular wave action. Ontogenetic series show isometric growth of the otoliths, and some specimens show growth rings on two orders of magnitude.     

Early and Middle Pleistocene river systems in eastern England: evidence from Leet Hill,southern Norfolk,England

Pleistocene sediments at Leet Hill, southern Norfolk are examined in terms of their sedimentary structures, palaeocurrent indicators, clast and heavy mineral lithology and litho- and morphostratigraphic position. Colour of the quartzite and vein-quartz clasts is used to differentiate the Bytham and the Kesgrave sands and gravels, with the Bytham sands and gravels having a significantly higher proportion of coloured material. The Kirby Cane sands and gravels are the lower sedimentary unit and were deposited by the Bytham river, which drained a catchment extending into central England. At Leet Hill, erosion of the Kesgrave Sands and Gravels by the Bytham river has given the Kirby Cane sands and gravels a distinctive lithological assemblage. Trace clast lithologies suggest that the Kesgrave Sands and Gravels in the region of Leet Hill were deposited in a coastal location with an input from northern sources as well as southern and Welsh sources diagnostic of the Thames catchment. The glaciofluvial Leet Hill Sands and Gravels were deposited by outwash from the Anglian Scandinavian ice sheet. Initially the flow direction of the outwash was determined by the Bytham river valley, but this changed to a southerly direction once the valley had been infilled. This paper provides the first indication of the location of the boundary (Early Pleistocene coastline) between the fluvial Kesgrave Sands and Gravels and the marine equivalent reworked by coastal processes, and demonstrates the way the pre-glacial relief initially controlled patterns of glaciofluvial sedimentation during the early part of the Anglian glaciation. Copyright © 1999 John Wiley & Sons, Ltd.     

The structural evolution of the Northern Hastings Block and southern Nambucca Block,southern New England Orogen,eastern Australia

The Hastings Block is a weakly cleaved and complexly folded and faulted terrain made up of Devonian, Carboniferous and Permian sedimentary and volcanic rocks. The map pattern of bedding suggests a major boundary exists that divides the Hastings Block into northern and southern parts. Bedding north of this boundary defines an upright box-like Parrabel Anticline that plunges gently northwest. Four cleavage/fold populations are recognised namely: E–W-striking, steeply dipping cleavage S₁ that is axial surface to gently to moderately E- or W-plunging; F₁ folds that were re-oriented during the formation of the Parrabel Anticline with less common N–S-trending, steeply dipping cleavage S₂, axial surface to gently to moderately N-plunging F₂ folds; poorly developed NW–SE-striking, steeply dipping cleavage S₃ axial surface to mesoscopic, mainly NW-plunging F₃ folds; and finally_, a weakly developed NE–SW-striking, steeply dipping S₄ cleavage formed axial surface to mainly NE-plunging F₄. The Parrabel Anticline is considered to have formed during the D₃ deformation. The more intense development of S₂ and S₃ on the western margin of the Northern Hastings Block reflects increasing strain related to major shortening of the sequences adjacent to the Tablelands Complex during the Hunter–Bowen Orogeny. The pattern of multiple deformation we have recorded is inconsistent with previous suggestions that the Hastings Block is part of an S-shaped orocline folded about near vertically plunging axes.     

皖南上震旦统蓝田组Ag地球化学特征研究

皖南地区上震旦统蓝田组,由黑色炭质页岩、泥灰岩和含Mn白云岩、白云质灰岩等组成,厚120～160m,是皖南Ag、Pb、Zn、Cu多金属矿的重要赋矿层位。研究结果表明,蓝田组Ag有明显富集,丰度493×10-9。蓝田组存在3个富Ag层段,且与Ag多金属矿床中的矿体分布是对应的;Ag的富集受制于缺氧环境或热水作用;Ag来源于陆源细碎屑以及热水沉积物;Ag的赋存方式与含Bi、Sb、Hg等矿物相关。     

Formation of siderite-Mg-calcite-iron sulphide concretions in intertidal marsh and sandflat sediments, north Norfolk, England

Concretions cemented mainly by siderite, Mg-calcite and iron monosulphide are common in late Holocene marsh and sandflat sediments on parts of the north Norfolk coast. Field experiments have shown that the concretions are actively forming in reduced sediments in which sulphate-reducing bacteria are active. δ¹³C values ranging from ?3 to ?11·8% (mean ?5·9%0) suggest that the carbonate in the concretions is derived partly from marine sources and partly from microbial degradation of organic matter. δ¹⁸O values ranged from ?6·4% to + 0·8% (mean ?1·0%) suggesting that carbonate precipitated in porewaters ranging from pure sea water to-sea water diluted with meteoric water. Chemical analysis of porewaters showed no evidence of significant sulphate depletion at the depth of concretion formation. Some concretions have formed around fragments of wood or metal, but others contain no apparent nucleus. In field experiments siderite, FeS and Mg-calcite were precipitated around several different nuclei within a period of six months. We suggest that siderite may form wherever the rate of iron reduction exceeds the rate of sulphate reduction, such that insufficient dissolved sulphide is available to precipitate all the available dissolved ferrous iron.     

The lignin geochemistry of marine sediments from the southern Washington coast

Lignin oxidation products and stable carbon isotope distributions are used to investigate the sources, transport, and chemical stability of land-derived organic matter in dated cores of modern sediment from the southern Washington State continental shelf and slope. There is no evidence for significant chemical alteration of lignin compounds in these sediments for time periods of up to 400 yr. Gymnosperm woods and nonwoody angiosperm tissues account for most of the land-derived organic matter in the deposits. These land plant remains have an average δ¹³C of approximately ?25.5% and are concentrated in a narrow band of silty sediment which extends northward from the Columbia River mouth along the mid-shelf. Marine organic matter having an approximate δ¹³C of ?21.5%, strongly predominates in most other shelf and slope environments. Net fluxes of land-derived organic matter into the surface 5 cm of the cores vary directly with sediment accumulation rates. Net fluxes of marine organic material into the surface sediments are highest in environments which favor the preservation of organic matter, but correspond to less than 1% of the primary productivity in the overlying waters.     

东天山石炭纪雅满苏组火山岩特征及地质意义

雅满苏组火山岩是东天山石炭纪火山岩的重要组成部分,也是东天山地区海相火山岩型铁多金属矿床的赋矿地层。其年代学及地球化学研究对探讨该区古生代构造演化和火山岩型铁多金属矿床成因具有重要意义。本文对东天山地区雅满苏组火山岩的岩石学、地球化学和同位素年代学进行了系统研究。结果显示:雅满苏组是一套海相火山岩夹碳酸盐岩建造,其上亚组英安岩的LA-ICP-MS锆石U-Pb年龄为334.4±1.7 Ma(MSWD=0.67),代表了雅满苏上亚组火山岩形成时代,切穿雅满苏铁矿区矽卡岩及矿体的正长岩的LA-ICP-MS锆石U-Pb年龄为325.5±1.7 Ma(MSWD=0.34),表明雅满苏铁矿床形成不晚于325 Ma。雅满苏上亚组英安岩和玄武岩显示了富集LREE、U、Sr,相对亏损Nb、Ta等元素的特征,且英安岩锆石的(176Hf/177Hf)i比值介于0.282 644~0.282 802之间,εHf(334 Ma)为3.0~8.0,表明它们是活动大陆边缘弧环境的产物,英安岩是新生地壳物质部分熔融的结果,玄武岩是软流圈地幔与受俯冲板片流体交代地幔的混合熔体演化的产物。结合前人研究成果,认为雅满苏组火山岩是早石炭世中期古亚洲洋俯冲作用的产物,石炭纪时期古亚洲洋尚未闭合,雅满苏铁矿床形成介于334~325 Ma之间,是与石炭纪火山岩有成因联系的铁矿床。