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.     

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.     

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.     

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.     

鄂尔多斯盆地西缘马家滩地区石盒子组砂岩的岩石学、地球化学与成岩作用特征

鄂尔多斯盆地马家滩地区石盒子组是天然气的重点勘探层位。对马家滩地区石盒子组的岩石学特征和成岩作用研究表明,石盒子组的储层岩石类型主要为石英砂岩、岩屑石英砂岩,少量的长石岩屑砂岩。储层砂岩的成岩作用类型主要有压实和压溶、石英次生加大、胶结、溶解。根据成岩作用特征,建立了研究区储层砂岩的成岩共生序列: 自生伊利石--自生绿泥石--石英次生加大--高岭石--方解石。鄂尔多斯盆地作为中国CO2 地下埋藏的潜在目标区,开展CO2 可能埋藏层段的岩石学特征和成岩作用研究,可为CO2 地质储存的数值模拟研究提供岩石学信息。     

The Green Castle Sandstone Formation: A new name for the Cwmffrwd Formation (Old Red Sandstone) preoccupied by an Ordovician Member

The Geological Survey’s Framework Report on the Old Red Sandstone of the Anglo-Welsh region includes a proposal for a new formational name, the Cwmffrwd Formation, for the basal formation of the Daugleddau Group in Carmarthenshire, S. Wales.The name is preoccupied by the Early Ordovician Cwmffrwd Member of the Carmarthen Formation and a new name, the Green Castle Sandstone Formation is proposed for the Cwmffrwd Formation.     

Pb-Pb age and Sr isotopic characteristic of the Middle Riphean phosphorite concretions: The Zigaza-Komarovo Formation of the South Urals

The Pb-Pb age of phosphorite concretions of the Zigaza-Komarovo Formation, which composes the intermediate horizons of the Riphean stratotype of the South Urals, was determined in fractions resulting from the stepwise dissolution of concretions in 0.1 N, 0.5 N, and 1 N HCl. The determination of the Sr isotopic composition in phosphate fractions was favorable for rejection the fractions polluted with extraneous material. On the ²⁰⁷Pb/²⁰⁴Pb-²⁰⁶Pb/²⁰⁴Pb diagram, the isochron based on 31 points corresponds to 1330 ± 20 Ma (MSWD = 1.12), which is in agreement with the stratigraphic position of the Zigaza-Komarovo Formation. The decreased μ₂ value of 9.57 for the phosphorite concretions relative to that of the average earthly lead based on the Stacey-Kramers model (9.74) is related to the rocks with an admixture of mantle lead, which occur in the run-off area of the Zigaza-Komarovo sediments.     

Mineralogy and geochemistry of atypical reduction spheroids from the Tumblagooda Sandstone,Western Australia

Reduction spheroids are small-scale, biogenic, redox-controlled, metal enrichments that occur within red beds globally. This study provides the first analysis of the compositionally unique reduction spheroids of the Tumblagooda Sandstone. The work aims to account for their composition and consequently improve existing models for reduction spheroids generally, which presently fail to account for the mineralogy of the Tumblagooda Sandstone reduction spheroids. Interstitial areas between detrital grains contained in the cores of these reduction spheroids are dominated by microplaty haematite, in addition to minor amounts of svanbergite, gorceixite, anatase, uraninite, monazite and illite. The haematite-rich composition, along with an absence of base metal phases and the vanadiferous mica roscoelite, makes these reduction spheroids notable in comparison to other global reduction spheroid occurrences. Analyses of illite crystallinity provide values for samples of the Tumblagooda Sandstone host rock corresponding to heating temperatures of ca 200°C. Consequently, while Tumblagooda Sandstone reduction spheroids formed via the typical metabolic processes of dissimilatory metal-reducing bacteria, the combination of a unique mineralogy and illite crystallinity analysis provides evidence of more complex late-stage heating and reoxidation. This has not previously been recognised in other reduction spheroids and therefore expands the existing model for reduction spheroid genesis by also considering the potential for late-stage alteration. As such, future reduction spheroid studies should consider the potential impact of post-formation modification, particularly where they are to be used as evidence of ancient microbial processes; such as in the search for early evidence of life in the geological record on Earth or other planets. Additionally, because of their potential for modification, reduction spheroids serve as a record of the redox history of red beds and their study could provide insights into the evolution of redox conditions within a given red bed during its diagenesis. Finally, this paper also provides insights into the relatively understudied diagenetic history of the Tumblagooda Sandstone; supplying the first reliable and narrow constraints on its thermal history. This has important implications for the thermal history of the Carnarvon Basin and its petroleum prospectivity more broadly.     

栖霞组沉积地球化学特征及其环境意义

沉积环境的古氧相特征是沉积环境和古海洋特征恢复的重要内容。岩石地球化学特征是判断其形成环境氧化还原条件的重要手段之一。本文以来宾地区铁桥面为重点．通过对栖霞组灰岩的地球化学分析，结合沉积学、古生态学特征．认为栖霞组沉积于贫氧的沉{只背景．是在海水深度和海域的局限程度等沉积条件发生周期性变化的情况下形成的。古氧相地球化学指标V(V十Ni)、Cc/La、U／Th值都适用于该组以钙质沉积为主的沉积物。黄铁矿矿化程度(DOP值)变。化较大．眨映该区多变的古氧相特征。     

The correlation and sequence architecture of the Ormskirk Sandstone Formation in the Triassic Sherwood Sandstone Group of the East Irish Sea Basin,NW England

The existing stratigraphic nomenclature applied to the Early and Middle Triassic Sherwood Sandstone Group in NW England has resulted from more than 150 years of geological investigation, but is characterized by a lithostratigraphic system that is insufficiently flexible to allow for variations in lithology and sedimentary facies within a continental depositional system. A revised well correlation based on the detrital mineralogical and chemical composition of the Ormskirk Sandstone Formation in four offshore wells, that is then extended to provide near‐basin‐wide well correlations using a regional shale marker, confirms previously suggested but unproven diachroneity at the top of the Sherwood Sandstone Group. It also reveals the presence of incised valleys filled by stacked amalgamated fluvial channel sandstones and cut into previously deposited aeolian and sandflat sequences as well as older fluvial channel sandstones. The combination of well correlations indicates that the valleys were incised by a fluvial system flowing NW from the Cheshire Basin into the East Irish Sea Basin and then west towards the Peel and Kish Bank basins. The stratal geometry of the upper part of the Sherwood Sandstone Group is suggested to conform to models of climatically mediated alternations of fluvial degradation and aggradation in response to changes in the relationship between sediment flux and stream discharge. This model is supported in the Sherwood Sandstone Group by climatically driven variations in the non‐channelized facies which record upward wetting and drying cycles that can be locally tied to fluvial incision surfaces, and suggest a hierarchy of at least three levels of climatic cyclicity recorded within the sedimentary succession. Copyright © 2006 John Wiley & Sons, Ltd.     

川东南地区志留系小河坝组砂岩特征及物源分析

通过对川东南地区小河坝组砂岩的碎屑组分、岩屑类型、重矿物组合、地球化学（稀土元素、微量元素）及古流向的研究,分析了小河坝组砂岩的物源方向、母岩类型及源区的构造背景。结果显示：源区为盆地东边江南－雪峰山隆起西侧上元古界板板溪群及其侵入板溪群中的基性岩体、中基性喷出岩体。具有活动大陆边缘、大陆岛弧及被动大陆边缘的构造背景。地球化学研究进一步证明,母岩主要为更老的沉积岩再旋回沉积物及少量岩浆岩。在早志留世小河坝期以华南板块缓慢向扬子板块蠕动方式相拼接,致使扬子板块整体缓慢抬升,同时沉积中心不断向西北方向迁移,造成研究区具有明显沉积旋回性的物源供给特征。     

Facies analysis and geochemistry of the Euphrates Formation in Central Iraq

The Euphrates Formation (Lower Miocene) in the Central Iraq consists mainly of shallow marine carbonates. Two hundred ten samples were collected from 21 wells (1E to 21ED) at Bahar Najaf area, and 18 samples were collected at Wadi Asadi in Baghdadi area, from Euphrates Formation. Four microfacies are identified, namely mudstone, wackestone, packstone, and rare grainstone with ten submicrofacies. The allochems in the Euphrates Formation are dominated by bioclasts. Peloids, ooids, and intraclasts are less abundant. The common fossils in the Euphrates Formation are miliolids, algae, ostracods, Miogypsina, and abundant shells of pelecypods and gastropods. Calcite and dolomite are the predominant mineral components of the Euphrates Formation. The carbonates of the Euphrates Formation have been affected by a variety of diagenetic processes such as micritization, dissolution, neomorphism, cementation, stylolitization, dolomitization, dedolomitization, and silicification. The Euphrates Formation was deposited in open to restricted platforms which indicated lagoonal environment with warm and restricted open circulation. In fact, prevalence and abundance of micrite provide an evidence of a shallow marine of low-energy environment and, in some places, may be approaching to be stagnant environment. The average of CaO in Najaf area (51.5 %) is slightly lower than that in Baghdadi area (53.3 %), which was reflected in calcite content found being 91 % in Najaf and 94 % in Baghdadi. Dolomite and gypsum appeared as minor minerals beside calcite, so low concentration of MgO (0.83 % in Najaf; 0.63 in Baghdadi) and SO₃ (0.55 % in Najaf; 0.53 % in Baghdadi) was reflected information of small amounts of dolomite (2 % in Najaf; 1.6 % in Baghdadi) and gypsum (0.7 % in Najaf and 0.6 in Baghdadi) in the Euphrates Formation. The insoluble residue in Najaf area (4.37 %) is relatively higher than that in Baghdadi area (1.9 %), indicating that the Euphrates Formation in Najaf Area has deposited in an environment closer to the shoreline. Concentrations of the trace elements Sr, Mn, and Fe which support the conclusion that reminds the Euphrates Formation had been deposited in a shallow marine environment of quiet energy, with the likelihood that the shoreline was the nearest to Najaf rather than to Baghdadi.     

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.     

鄂尔多斯盆地北部直罗组黄铁矿与砂岩型铀矿化关系研究

鄂尔多斯盆地东北部是我国砂岩型铀矿重要成矿区。通过对盆地北部大营铀矿床直罗组赋矿地层砂岩野外观察、镜下鉴定发现,黄铁矿存在多种产状,它们的宏观、镜下产状存在一定对应关系。对黄铁矿硫同位素的分析测试以及蚀变矿物的研究发现,δ~(34)S的变化范围-36.5‰~-27.3‰,平均值为-32.28‰,为较小的负值,具有明显生物成因作用。同时草莓状黄铁矿以及生物碎屑胞腔中的铀矿物的发现,也证实了铀成矿期的生物作用。地下水中U~(6+)、Fe~(2+)与"轻"的H_2~(32)S发生氧化还原反应,从而形成了黄铁矿与铀矿的紧密伴生的现象。     

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.     

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。     

Paleosol geochemistry of the late Paleocene Goler Formation of Southern California

Paleosol (fossilized soil) geochemistry can provide a record of paleoclimatic conditions due to the relationships between pedogenic processes and climate. In this study, paleosols from the late Paleocene Goler Formation of Southern California were used to determine the paleoclimatic conditions active during pedogenesis. The enrichment and retention of soluble elements (Ca, Mg and Na) and the mobilization of Fe and Mn within the paleosol profiles suggest a climate with strongly seasonal precipitation. Similarly, variations in the Mn content and δ¹³C ratio of pedogenic carbonate nodules also reflect seasonal precipitation. Regional paleotopography was likely an important control on the paleoclimate of the Goler Formation due to rain shadow effects. Although the size and location of these ancient mountains are poorly constrained, the identification of climatic effects specifically associated with these variables provides new constraints.