Carbon,oxygen and sulphur isotope variations in concretions from the Upper Lias of N.E. England

Carbon, oxygen and sulphur isotope data for transects across two pyrite-bearmg carbonate concretions, and their host sediments, from the Upper Lias of N.E. England show symmetrical zonation. δ¹³C_PDB values of the calcite cement (?12.9 to ?15.4%.) indicate that most of it originated from organic matter by bacterial reduction of sulphate, augmented with marine and, to a lesser extent, fermentation derived carbonate. Organic carbon (δ¹³C_PDB = ?26.1 to ?37.0%.). reflects the admixture of allochtho-nous terrestrial organic matter with marine material and the selective preservation of isotopically light organic material through microbiological degradation.Two phases of pyrite are present in each concretion. The earlier framboidal pyrite formed throughout the sediment prior to concretionary growth and has δ³⁴S_CD values of ?22 to ?26%. indicating formation by open system sulphate reduction. The later euhedral phase is more abundant and reaches values of ? 2.5 to ? 5.5%. at concretion margins. This phase of sulphate reduction provided the carbonate source for concretionary growth and occurred in a partially closed system. The δ¹³C and δ³⁴S data are consistent with mineralogical and chemical evidence which suggest that both concretions formed close to the sediment surface. The δ₁₈O values of the calcite in one concretion (δ¹⁸O_PDB = 2.3 to ?4.8%.) indicate precipitation in pore waters whose temperature and isotopic composition was close to that of overlying seawater. The other concretion is isotopically much lighter (δ¹⁸O_PDB?8.9 to ?9.9%.) and large δ¹⁸O differences between concretions in closely-spaced horizons imply that local factors control the isotopic composition of pore waters.     

贵州关岭上三叠统瓦窑组中碳酸盐岩结核形成的生物作用

贵州省关岭县新铺乡附近的晚三叠世早期地层瓦窑组底部产具重大科学意义的关岭生物群。关岭生物群产出地层中伴有大量大型碳酸盐岩结核。这些结核中部都有植物茎干,结核内的海百合、双壳、菊石、牙形刺等生物化石含量明显高于结核周围的岩石,且有许多生物化石直接附着在植物茎干上。这类结核的形成,除化学沉积作用外,还有生物作用的影响。海百合、双壳类和菊石类栖息在植物茎干上营假浮游生活,随着栖息生物量和化学沉积物灰泥的增加,逐渐沉积在海底形成结核。     

The role of diagenetic carbonate concretions in the preservation of the original sedimentary record

The Upper Cretaceous organic rich limestones and marls of the Tarfaya basin of southwest Morocco contain numerous calcite concretions, which formed during early diagenesis. Relative textural similarities are observed both in the concretions and in the host sediments. However, the biological content of the concretions is considerably higher than in the host marls and limestones. Evidence for fossil dissolution in the host marls, and the absence of concretions in some fossil-rich zones, suggest that the difference in fossil abundance between the concretions and host rock is a function of dissolution, rather than preferential precipitation in fossil-rich areas. Consequently, the carbonate concretions appear to represent the 'memory' of the sediment and allow quantification of the original biological components and are potential tools for estimating the original biological material deposited in the soft sediments.     

鄂尔多斯盆地渭北地区上三叠统延长组长7油层组碳酸盐结核中自生碳酸盐矿物的特征

早期形成的碳酸盐结核在埋藏期间会经历多种碳酸盐矿物相沉淀的复杂胶结作用,岩石学研究是探究结核成因的关键。通过野外剖面观察、岩石学观察和阴极发光技术,分析了鄂尔多斯盆地渭北地区上三叠统延长组长7油层组泥页岩中各种形状的方解石和白云石结核中自生碳酸盐矿物的特征。这些结核为成岩早期的产物,构成结核的自生碳酸盐矿物特征显著:(1)球粒方解石结核中,方解石呈纤维状或刃片状,球粒间充填晶粒方解石或因压实呈贴面结合,纤维状方解石发桔红色和暗红色2种光,刃片状方解石发暗红色光;(2)粉晶方解石结核中,方解石呈他形粒状,含有机质包裹体或纤维状晶形残余,晶间含沥青和纤维状方解石残余,主要发暗红色光;(3)白云石结核有泥晶和粉晶2种晶体类型,粉晶白云石结核含较多泥质,泥质条带或有机质条带处常见纤柱状白云石;(4)沿裂缝充填的方解石和白云石常呈纤维状或纤柱状结构,发暗红色光或不发光。研究区长7油层组碳酸盐结核中的方解石和白云石具有不同的成因类型和复杂的胶结作用:球粒方解石和泥晶白云石代表了结核开始形成时的胶结作用,可以准确地反映结核的成因;粉晶方解石、粉晶白云石反映了交代成因;裂缝中纤维状、纤柱状方解石和白云石集合体则为结核经历了较强压实作用之后充填裂缝而成。     

Stable oxygen and carbon isotopes of carbonate concretions of the Miocene Yeonil Group in the Pohang Basin,Korea: Types of concretions and formation condition

Carbonate concretions in the Miocene sedimentary rocks of the Yeonil Group in the Pohang Basin (Korea) were investigated in terms of stable oxygen and carbon isotope composition to delineate the origin and associated diagenetic environment for their formation. Carbonate concretions are widely distributed in all the sedimentary rocks in the Pohang Basin, showing that the calcitic concretions are preserved within the mass-flow deposits and the dolomitic ones mostly in the hemipelagic siliceous rocks (diatomites). Concretions can be classified into four different types, on the basis of the stable isotopic signatures, each of which represents its own geochemical range.Type I concretions are calcitic and are composed of micrite to microspar. They occur in the conglomerates and sandstones which were deposited by mass flows (debris flow to turbidity current). It shows relatively lower δ¹⁸O (− 14.0 to − 9.3‰) and δ¹³C (− 19.6 to − 8.4‰) values. These concretions grew in a sulfate reducing zone under the influence of residual ambient seawater which had been significantly modified by volcanogenic sediments. Type II concretions are also calcitic, composed mostly of micrite with minor microspar and found in the sandstones. These concretions are characterized by relatively high δ¹⁸O (+ 1.8 to + 2.4‰) and variable δ¹³C (− 17.3 to − 0.4‰) values. These isotopic signatures reflect that Type II concretions formed from just beneath the sediment/water interface down to the sulfate reducing zone through the early stage of methanogenesis. Type III concretions are also calcitic, and composed largely of micrite with a minor contribution of microspar. They are observed in hemipelagic mudrocks which were deposited under the influence of mass flows. They are characterized by intermediate to high δ¹⁸O (− 4.6 to + 1.6‰) and high δ¹³C (− 1.3 to + 8.8‰) values. These concretions grew in a methanogenic zone by residual ambient seawater and/or seawater slightly modified by reaction with volcanogenic sediments. Type IV concretions are dolomite with calcite inclusion, and occur in hemipelagic siliceous rocks. These concretions are mostly composed of micrite and characterized by variable δ¹⁸O (− 9.1 to + 0.7‰) and high δ¹³C (+ 3.1 to + 17.9‰) values, suggesting formation in the methanogenic zone, although the residual ambient seawater is slightly modified by volcanogenic sediments.The same type of the concretions is widely distributed throughout the basin and always shows its own distinctive stable isotopic signature. This means that the formation of the given type depends upon the lithology and composition of host sediments that are closely related to the depositional process of the fan-delta systems regardless of their localities. Further, the different types of concretions are also found at the different, but closely spaced stratigraphic levels in the same locality, displaying the distinctive diagenetic conditions for each type. Such preservation of the unique diagenetic signatures in individual type of concretion suggests that the concretions formed in a completely closed diagenetic system. Therefore, caution should be made to simplify and generalize the diagenetic condition for the formation of any concretions in a large sedimentary basin.     

Muddy deltas in freshwater lakes, and tectonism in the Upper Carboniferous Coalfield of NE England

ABSTRACT
The Westphalian B sediments of NE England were deposited on part of a coastal plain with subdued relief. Most of the fine-grained sediments were deposited by small fluvially dominated muddy deltas which fed into shallow freshwater lakes in tectonic depressions a few metres deep and a few tens of kilometres across.
Coalfield lakes contained an abundant low-diversity bivalve fauna and existed for thousands of years before delta infill. Pro-delta clay rhythmites, formed by flood turbidites, coarsened up into wide silty mouth bars, which merged up into channel mouth sands, inversely-graded subaqueous levee deposits and sandy channel fills. Delta complexes were either abandoned below water level leaving a lake, or were colonized by plants, which resulted in trapping of suspended sediment and build-up of a seatearth to near water level when peats could accumulate. These swamps were analogous to the present raised bogs of Indonesia and had a lateral zonation of vegetation to a central low-diversity flora. Upwards reversal of this zonation and the succession of coals by lake sediments show that peat floras were killed by drowning due to rapid tectonic subsidence. Subsurface data show that seam splits and sand-body locations were tectonically controlled, and that the lake deltas in this area were distant from any major sand distributary.     

Stable isotopes, chemistry and petrology of carbonate concretions (Mishash formation, Israel)

Carbonate concretions of variable sizes occur in the upper member of the Senonian (Upper Cretaceous) Mishash formation in Israel. Eight concretions and their surrounding country rocks were examined in the field, in thin sections and by X-rays. The isotopic composition of carbon and oxygen in the carbonates, the amount of acid insoluble residue, as well as the concentrations of P₂O₅, Ca, Mg, Sr and Fe were determined. Other concretions and country rocks were analyzed for oxygen and carbon isotopes only.

The concretions are composed of almost pure, microsparitic calcite, whereas the country rocks are porcellanitic-phosphoritic chalks. Compared with the surrounding rocks, the concretions are strongly enriched in ¹²C and are depeleted in insoluble residue, P₂O₅, SiO₂, Fe, Sr and Mg.

It is postulated that the concretions were formed by addition of CaCO₃ to sites of anaerobic decomposition of organic matter, while CaCO₃ was mobilized in the surrounding sediments, in which aerobic decomposition of organic matter prevailed.

Several consequences of this model are considered, concerning the quantitative volume changes, as well as the distribution of SiO₂ and Mg between concretions and country rocks.     

鄂尔多斯盆地中上三叠统延长组长7段碳酸盐结核成因讨论

鄂尔多斯盆地南部铜川地区露头区中三叠统延长组长7段细砂岩、粉砂岩、泥质粉砂岩、粉砂质泥岩层序中发育有大量圆球状、椭球状、扁球状碳酸盐岩结核,对于其成因存在争议.对铜川地区多个剖面的结核开展宏观描述,在微观薄片观察基础上开展岩石矿物组成、稳定同位素、簇同位素以及微区同位素等分析,特别是选取一个结核开展了详细的解剖.结果显示结核成分以方解石为主,少量白云石;内部结构有差异,在球体横切面上明显分为两个圈层;碳同位素值正偏,由内部圈层向外部圈层降低;氧同位素与碳同位素变化趋势一致,计算结核形成古温度变化区间为28.6～76.5℃;簇同位素揭示结核中部形成温度为42.9℃.认为该类结核为早期发酵带内细菌参与甲烷生成作用形成,甲烷菌活动引起有机质碳同位素分馏,碳酸盐结核中方解石和白云石圆球粒可能是蓝细菌细胞方解石化或白云石化的结果.根据埋藏史,认为该类结核形成于成岩作用早期,后期在成岩过程中叠加生长,同心环层结构明显.     

Evidence for surface reaction-controlled growth of carbonate concretions in shales

Estimates for the rate of concretionary growth in shales are based on models which assume that growth is diffusion-controlled. However, laboratory and field studies of CaCO₃ precipitation in organic carbon-rich sediments indicate that surface reactions control growth, due to inhibition by various dissolved species. The spatial distribution of carbonate concretions in the Jet Rock (Lower Jurassic, England) is also inconsistent with diffusion-controlled precipitation of CaCO³ into concretions, and growth must have been at least partly surface reaction-controlled.     

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.     

The geochemistry of concretions from the Kimmeridge Clay Formation of southern and eastern England

Concretions from the Kimmeridge Clay Formation are of three types: calcareous concretions, septarian calcareous concretions and pyrite/calcite concretions and nodules, which occur within different mudstone facies. Isotopic and chemical analysis of the concretionary carbonates indicate growth in the Fe-reduction, sulphate-reduction and decarboxylation zones. The septarian concretions show a long and complex history, with early initiation of growth and development spanning several phases of burial, each often resulting in the formation of septaria. Growth apparently ceased in the transitional zone between the sulphate-reduction and the methanogenesis zones. Very early growth in the Fe-reduction zones is also seen in one sample. The non-septarian concretions began growth later within the sulphate-reduction zone and have had a simpler burial history while the pyrite/calcite concretions show carbonate cementation in the sulphate-reduction-methanogenesis transition zone. A ferroan dolomite/calcite septarian nodule with decarboxylation zone characteristics also occurs. Development of concretions appears to be indirectly controlled by the sedimentation rate and depositional environment, the latter determining the organic matter input to the sediments. Calcareous concretions predominate in swell areas and during periods of low sedimentation rate in the basins with poor organic matter preservation and deposition of calcareous mudstones. Pyrite/calcite concretions occur in organic-rich mudstones deposited under higher sedimentation rates in the basins, while the ferroan dolomite nodule grew under very high sedimentation rates.     

Upper delta plain lacustrine and fluviolacustrine facies from the Westphalian of the Durham coalfield, NE England

Facies analysis suggests that the productive Westphalian (Upper Carboniferous) Coal Measures of the Durham coalfield in NE England were deposited on an upper delta plain. Distributary channels crossed the plain and were separated by shallow lakes. Detailed examination of largely three-dimensional exposures has revealed the existence of nine laterally and vertically interrelated fluviolacustrine and lacustrine lithofacies. Facies 1 and 2 are interpreted as overbank deposits of distributary channels, Facies 3–5 are regarded as deposits of crevasse splay/minor delta systems, and Facies 6–9 are considered to have formed in areas of diminished clastic sediment supply. Facies 4 and 5 are volumetrically the most important. Facies 3–9 are interpreted as representing progressively less energetic conditions of sedimentation across a lake, from the point of entry of a crevasse splay/minor delta system. The distribution and characteristics of the lithofacies indicate that the upper delta plain lakes were completely or effectively enclosed, up to about 8m deep and had wave fetches of the order of 20 km. These lakes were intermittently infilled by the crevasse-initiated, minor delta systems and, to a relatively minor extent, by overbank flood sediment from channels. Infilled lake surfaces became platforms for plant colonization and peat accumulation. The three dimensional relationships of the various lithofacies provide a model of Coal Measure lacustrine sedimentation, which may have wider implications in extending the model of interdistributary genesis and infilling proposed by Elliott, particularly with respect to detailed facies relationships and to the balance between overbank and crevasse-derived sediment.     

Strontium isotope composition of the lower proterozoic carbonate concretions: The Zaonega Formation,Southeast Karelia

The middle part of the volcanosedimentary Zaonega Formation of the Ludikovian Suprahorizon (approximately 2.0 Ga) includes large carbonates concretions and lenses in shungite layers. Carbonate lenses and concretions are primarily elongated and flattened, and their thickness varies from tens of centimeters to a few meters. Some lenses retain relicts of lamination. Concretions are composed of calcite or dolomite. They contain abundant organic matter, as well as mica, talc, chlorite, quartz, and pyrite crystals. The calcite concretions contain some dolomite admixture (Mg/Ca = 0.011?0.045) and differ from sedimentary limestones by a low Fe/Mn value (0.3–2.1). The Sr content is as much as 385–505 μg/g in most samples and is low (86 μg/g) only in one sample. The Rb-Sr systematics of carbonate concretions was studied with the stepwise dissolution procedure, which included processing with the ammonium acetate solution (AMA fraction) to partially remove the secondary carbonate material, with dissolution of the residue in acetic acid (ACA fraction). In individual calcite samples, discrepancy between the measured ⁸⁷Sr/⁸⁶Sr values in the AMA and ACA calcite fractions shows a variation range of 0.0008–0.0033. The initial ⁸⁷Sr/⁸⁶Sr ratio in the ACA fractions of the studied samples varies from 0.7053 to 0.7162. The ratio shows a positive correlation with Mg/Ca and the proportion of siliciclastic admixture and negative correlation with the Mn content. The concretions were formed when the sediments subsided, probably, during the transition from a zone with “mild” reductive conditions to zones with active sulfate reduction and methanogenesis. In the sulfate reduction zone, where most pyrite-bearing concretions were formed, the sediment was not geochemically exchaged with the bottom water and was evolved into a closed or semiclosed system. Processes of diagenesis in this zone promoted the release of the radiogenic ⁸⁷Sr from the associated siliciclastic minerals, resulting in growth of the initial ⁸⁷Sr/⁸⁶Sr in concretions up to 0.7108–0.7162. Some calcite concretions, which lacked pyrite (or contained its minimal amount) were likely formed in a thin surficial sediment layer located above the sulfate reduction zone. Therefore, they precipitated Sr in isotope equilibrium with Sr of the bottom water. However, large concretions and carbonate lenses with an insignificant siliciclastic admixture could retain the signature of early diagenesis or even sedimentation. The initial ⁸⁷Sr/⁸⁶Sr ratio in one of such samples with the siliciclastic admixture of 6.2% makes it possible to estimate the maximal value of this ratio (0.7053) in the Ludikovian paleobasin.     

Ironstones in the Upper Oxfordian of southern England

The Upper Calcareous Grit, the last of the four upward shallowing cycles that comprise the Corallian Beds of southern England, is relatively enriched in iron minerals, having local developments of chamosite oolite mudstone and much more widespread deposits of sand and mud containing variable amounts of siderite and disseminated chamosite. The chamosite oolite mudstones have a restricted fauna dominated by oysters and probably accumulated in slightly hyposaline lagoons where the ooids formed from mixed iron-, alumina- and silica-bearing gels. Siderite was produced during diagenesis from iron carried on the surface of clay minerals. This intimate association with the terrigenous clay fraction means that siderite occurs in sediments deposited in a variety of environments ranging from offshore shelf to lagoonal. The most important factor responsible for ironstone development was a very low rate of clastic supply throughout Upper Calcareous Grit times. The iron was probably derived by normal processes of weathering and erosion of sedimentary rocks exposed around the basin margin, but this cannot be conclusively proved and quite different iron sources may have been involved.     

Stratigraphic correlation of presumed Milankovitch cycles in the Blue Lias (Hettangian to earliest Sinemurian), England

Simple digital filtering methods allow the correlation of patterns of metre-scale cycles between outcrop sections and well logs through the Hettangian to earliest Sinemurian part of the Lower Lias in southern England. The matching of cyclic patterns is sufficiently confident to allow the identification of a significant break in the Blue Lias section at Lyme Regis (Dorset). The standard ammonite zones of the Hettangian Stage are shown to be of quantifiably unequal duration.     

新元古代帽碳酸盐岩中帐篷状构造的成因

帐篷构造是碳酸盐岩中的一种特殊沉积组构,因其倒“V”字形形态类似于帐篷(tepee)而得名,被认为是一种无成因意义的沉积组构。传统的帐篷构造在海相至陆相碳酸盐岩中都有发育,形态和胶结物的不同反映了沉积环境的变化,其成因为裂隙填充的胶结物结晶膨胀导致层面突起变形。新元古代帽碳酸盐岩中广泛发育有倒“V”字形的类似构造,但由于形态和成因上都和传统的帐篷构造有所区别,被称为“帐篷状构造”(te-pee-likestructure)。目前其成因解释主要有:“巨风暴潮波痕”、“甲烷气体渗漏”、“地下水侵位”和“晶体结晶”的假说。由于帐篷状构造的形成过程与机制和帽碳酸盐岩的成因密切相关,对帐篷状构造的进一步研究必将帮助我们对新元古代冰期结束机制的理解。     

Constraining pathways of microbial mediation for carbonate concretions of the Miocene Monterey Formation using carbonate-associated sulfate

Carbonate concretions can form as a result of organic matter degradation within sediments. However, the ability to determine specific processes and timing relationships to particular concretions has remained elusive. Previously employed proxies (e.g., carbon and oxygen isotopes) cannot uniquely distinguish among diagenetic alkalinity sources generated by microbial oxidation of organic matter using oxygen, nitrate, metal oxides, and sulfate as electron acceptors, in addition to degradation by thermal decarboxylation. Here, we employ concentrations of carbonate-associated sulfate (CAS) and δ³⁴S_CAS (along with more traditional approaches) to determine the specific nature of concretion authigenesis within the Miocene Monterey Formation.Integrated geochemical analyses reveal that at least three specific organo-diagenetic reaction pathways can be tied to concretion formation and that these reactions are largely sample-site specific. One calcitic concretion from the Phosphatic Shale Member at Naples Beach yields δ³⁴S_CAS values near Miocene seawater sulfate (～+22‰ VCDT), abundant CAS (ca. 1000 ppm), depleted δ¹³C_carb (～?11‰ VPDB), and very low concentrations of Fe (ca. 700 ppm) and Mn (ca. 15 ppm)—characteristics most consistent with shallow formation in association with organic matter degradation by nitrate, iron-oxides and/or minor sulfate reduction. Cemented concretionary layers of the Phosphatic Shale Member at Shell Beach display elevated δ³⁴S_CAS (up to ～+37‰), CAS concentrations of ～600 ppm, mildly depleted δ¹³C_carb (～?6‰), moderate amounts of Mn (ca. 250 ppm), and relatively low Fe (ca. 1700 ppm), indicative of formation in sediments dominated by sulfate reduction. Finally, concretions within a siliceous host at Montaña de Oro and Naples Beach show minimal CAS concentrations, positive δ¹³C values, and the highest concentrations of Fe (ca. 11,300 ppm) and Mn (ca. 440 ppm), consistent with formation in sediments experiencing methanogenesis in a highly reducing environment. This study highlights the promise in combining CAS analysis with more traditional techniques to differentiate among diagenetic reactions as preserved in the geologic record and shows potential for unraveling subsurface biospheric processes in ancient samples with a high degree of specificity.