Jurassic septarian concretions from NW Scotland record interdependent bacterial, physical and chemical processes of marine mudrock diagenesis

Septarian concretions in the Staffin Shales Formation (Kimmeridgian, Isle of Skye) allow controls on concretion rheology and septarian cracking to be investigated. Stratabound concretions consist of anhedral ferroan calcite microspar enclosing clay and minor pyrite. Intergranular volumes range from 77% to 88%, and calcite δ¹³C and δ¹⁸O values in most concretion bodies range from ?10·0‰ to ?17·3‰ and +0·3‰ to ?0·6‰ respectively, consistent with rapid and pervasive cementation in marine pore fluids. Septarian rupture occurred during incipient cementation, with a sediment volume reduction of up to 43%. Crack‐lining brown fibrous calcite records pore fluid re‐oxygenation during a depositional hiatus, followed by increasing Fe content and δ¹³C related to bacterial methanogenesis. Brown colouration results from an included gel‐like polar organic fraction that probably represents bacterially degraded biomass. A new hypothesis for concretion growth and septarian cracking argues that quasi‐rigid ‘proto‐concretions’ formed via binding of flocculated clays by bacterial extracellular polysaccharide substances (EPS). This provided rheological and chemical conditions for tensional failure, subcritical crack growth, volume contraction, calcite nucleation, and incorporation of degraded products into crack‐lining cements. Bacterial decay of EPS and syneresis of host muds provided internal stresses to initiate rupture at shallow burial. Development of septarian (shrinkage) cracks in muds is envisaged to require pervasive in situ bacterial colonization, and to depend on rates of carbonate precipitation versus EPS degradation and syneresis. Subsequent modification of septarian concretions included envelopment by siderite and calcite microspar, hydraulic fracturing associated with Cretaceous shallow burial or Palaeogene uplift; and cementation by strongly ferroan, yellow sparry calcite that records meteoric water invasion of the host mudrocks. An abundance of fatty acids in these spars indicates aqueous transport of organic breakdown products, and δ¹³C data suggest a predominantly methanogenic bicarbonate source. However, the wide δ¹⁸O range for petrographically identical cement (?1·3‰ to ?15·6‰) is difficult to explain.     

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.     

Reworked early diagenetic concretions and the bioerosional origin of a regional discontinuity within British Jurassic marine mudstones

The Coinstone is a well known hiatus-concretion level in the Lower Lias (Lower Jurassic, Upper Sinemurian) of Dorset, southern England. It has long been recognized as a layer of bored and encrusted, early diagenetic, clay-hosted septarian concretions coincident with a biostratigraphic gap of three ammonite subzones. Several different types of concretion of variable complexity can be distinguished, of which two, probably derived from slightly different stratigraphic levels, have been juxtaposed by condensation at the erosion surface. Diagenetic and biological processes occurring before, during and after exhumation on the Jurassic sea-floor can be recognized. The relative timing of these events can be distinguished, suggesting that initial concretion consolidation, the first generation of septarian cracking, and the precipitation of the first generation of crack-lining calcite preceded exhumation. These, therefore, probably took place at an early stage, at shallow burial depths within the accumulating sediment pile. The early calcite is brown, UV-fluorescent and inclusion-rich, and is similar to the first calcite generations seen in many other clay-hosted septarian concretions. A generally early diagnetic origin of this material is thus inferred. Observations on crack textures and geometries and the interactions of the post-exhumation fauna of encrusters, borers and burrowers lend support to previous suggestions that initial cracking in some septarian concretions took place in a stiff rather than a fully rigid concretion body, possibly given coherence by initial growth of some organic substance that was only later replaced by the calcite cements seen in most such concretions today. The burrowing activities of a benthic fauna in muds cause resuspension of sediment and facilitate erosion, even in the absence of high energy physical processes. Regional stratigraphic gaps may be formed as a consequence of sea level rises or falls, or as a response to sediment supply reduction independent of sea level change. Such major episodes of biologically mediated erosion in mudstone sequences may be of more general importance than has hitherto been recognized.     

Isotopic constraints on growth conditions of multiphase calcite–pyrite–barite concretions in Carboniferous mudstones

Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ¹³C=?28·7‰ PDB and δ¹⁸O=?1·6‰ PDB through to δ¹³C=?6·9‰ PDB and δ¹⁸O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ¹³C=?12·0 to ?10·1‰ PDB and δ¹⁸O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ³⁴S=+24·8‰ CDT and δ¹⁸O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ³⁴S=+6 to +11‰ CDT and δ¹⁸O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.     

Genesis and diagenesis of hiatus- and breccia-concretions from the mid-Cretaceous of Texas and northern Mexico

A study of septarian concretions from late Cretaceous shale sequences of Texas and northern Mexico reveals complex burial-exhumation histories. First generation concretions and pre-fossilized moulds formed in silty clays before significant compaction occurred. Syneresis cracks developed and were filled by length slow fibrous calcite with a decrease in iron content toward the centre of each vein; in some cases this was succeeded by growth of equant or bladed calcite. Subsequent erosion of enclosing sediment caused collapse and break up of concretions, leaving fragments and some unbroken concretions exposed to encrustation and boring on the sea floor. These were subsequently buried and enclosed in a second generation of concretions, which also developed syneresis cracks. The calcite that filled these latter cracks was generally bladed (sometimes followed by equant calcite) and contains more iron toward the centre of the vein. Differences between the calcite filling first and second generation septarian veins indicates changing diagenetic regimes during burial in the marine environment, without a major shift in diagenetic conditions, such as the introduction of meteoric waters. These conclusions have significant implications to cementation in ancient limestones, which show textural and chemical sequences similar to those present in the septarian concretions described.     

Significance of localized pore pressures to the genesis of septarian concretions

The burial-stress and hydrologic conditions existing during concretion formation in mudrocks are evaluated and integrated into a model for the genesis of septarian cracks. Initial concretion cement formation will lower concretion permeability through the filling of pre-existing pore space. During progressive burial, this may lead to increased excess pore pressure, localized within the concretion body causing a reduction of the effective stress. Analysis of the stress conditions and crack morphology suggests that cracks in septarian concretions result from tensional failure (sub-critical crack growth), as a consequence of this localized excess pore pressure. Conditions suitable for crack formation will depend upon the magnitude of the excess pore pressure and the stress corrosion limit of the concretion body. A review of the likely strength of such concretions indicates that cracking could be initiated at depths less than 10 m. A variety of observed crack morphologies can be explained with this model, depending upon the spatial distribution of strength and effective stress in the concretion. Crack orientations mostly reflect stress anisotropy, but are also influenced by directional anisotropy in the crack growth rates. Locally increased pore pressure also likely occurs in non-septarian concretions, but is not sufficient to cause cracking. This enhanced local pressure may assist the crystal surface growth reactions of the carbonate cement. Through this enhancement process, the shape of concretions may be a response to the local anisotropic pore-pressure contours, which reflect the permeability anisotropy of the concretion and surrounding mudrock.     

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.     

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。     

Injection clastic dykes in the Lower Oxford Clay (Jurassic) of central England: relationship to compaction and concretion formation

An injection dyke of fine-grained sandstone derived from the Kellaways Sand Formation intrudes overlying organic-rich shales and shell beds of the Lower Oxford Clay. The dyke shows cross-cutting relationships with early carbonate concretions, and fills uncompacted kosmoceratid ammonite shells both within the concretions and surrounding shales. Internally the dyke displays flow-like features, and the walls show lobate flow structures. Clasts of uncompacted Lower Oxford Clay and fragments of pyrite-rich concretions occur within the sandstone intrusions. The sandstone of the dyke was cemented by calcite identical to that precipitated in septarian cracks in the concretions. This cementation took place prior to final compaction of the Oxford Clay. The dyke has a sub-parallel relationship to the nearby Tinwell-Marholm fault suggesting that the dyke may be related to local tectonic events during the Middle Jurassic.     

Giant calcite-cemented concretions, Dakota Formation, central Kansas, USA

Giant spheroidal concretions (cannonball concretions; some nearly 6 m in diameter) in fluvial channel‐fill sandstones at two localities of the Dakota Sandstone formed by import of cement constituents at a burial depth of <1 km. During cannonball concretion growth a self‐organizational process restricted concretions to a relatively few but widely spaced, and locally, evenly spaced, sites. Other forms of calcite cements at these localities are cement patches in the form of intergrown grape‐size concretions (grapestone), and, locally, pervasive cement. An early episode of invasion by thermogenically generated H₂S, which reacted with iron oxides on detrital grains, generated scattered pyrite crystals and decimetre‐scale spheroidal pyrite concretions. Intergranular volumes (IGV) in the concretions range from 36% to 27%. The absence of a trend in IGV and of carbon and oxygen‐isotope ratios from cannonball centres to margins indicates that these concretions did not cement progressively outwards from the centre. Rather, the modern spheres represent the spatial extent of nucleation sites that were not otherwise organized within that volume. Carbon and oxygen‐isotope values for concretion calcites plot along a swath between depleted values of δ18C of ?36‰ and δ18O of ?13‰ and enriched values of ?4‰ and ?6‰, respectively. Four groups of calcites are evident on the basis of trace‐element content and suggest that the calcite precipitated across a range of oxidation conditions that do not correlate strongly with the isotopic compositions. Although fluvial overbank sandstones have some pedogenic calcite, the channel sandstones have at most a trace of pedogenic calcite and carbonate rock fragments, so that the bulk of cement components were imported to the sandstones. Carbon and calcium sources for calcite cement include marine limestone, carbonate shells, and anhydrite in addition to HCO derived from oxidized methane, most likely derived from beds underlying or laterally in communication with Dakota sandstones. HCO in ascending formation waters, released during compaction, mixed with meteoric water whose temperature and composition varied with time, to generate the 7‰ range in δ18O_calcite values measured.     

Microbial lipids of an intertidal sediment—I. Fatty acids and hydrocarbons

A detailed study has been made of the solvent extractable monocarboxylic, dicarboxylic and hydroxylated fatty acids and n-alkanes in a surface intertidal sediment, and the distributions compared to microorganisms cultured from the sediment. Diatoms are shown to contribute most of the monocarboxylic acids, particularly the significant amounts of polyunsaturated acids present, and a small proportion of the n-alkanes. Bacteria contribute between 11 and 14% of the monocarboxylic acids and markers for this, including trans-monounsaturated acids, are proposed. Detritus from the sea-grass Zostera muelleri is a major source of the α-hydroxy-, ω-hydroxy and α,ω-dicarboxylic acids in the sediment and a minor contributor of n-alkanes and long-chain fatty acids.     

Low-Mg calcite marine cement in Cretaceous turbidites: origin, spatial distribution and relationship to seawater chemistry

Lower Cretaceous (Hauterivian) bioclastic sandstone turbidites in the Scapa Member (North Sea Basin) were extensively cemented by low-Mg calcite spars, initially as rim cements and subsequently as concretions. Five petrographically distinct cement stages form a consistent paragenetic sequence across the Scapa Field. The dominant and pervasive second cement stage accounts for the majority of concretions, and is the focus of this study. Stable-isotope characterization of the cement is hampered by the presence of calcitic bioclasts and of later cements in sponge spicule moulds throughout the concretions. Nevertheless, trends from whole-rock data, augmented by cement separates from synlithification fractures, indicate an early calcite δ¹⁸O value of+0·5 to -1·5‰ PDB. As such, the calcite probably precipitated from marine pore fluids shortly after turbidite deposition. Carbon isotopes (δ¹³C=0 to -2‰ PDB) and petrographic data indicate that calcite formed as a consequence of bioclastic aragonite dissolution. Textural integrity of calcitic nannoplankton in the sandstones demonstrates that pore fluids remained at or above calcite saturation, as expected for a mineral-controlled transformation. Electron probe microanalyses demonstrate that early calcite cement contains <2 mol% MgCO₃, despite its marine parentage. Production of this cement is ascribed to a combination of an elevated aragonite saturation depth and a lowered marine Mg²⁺/Ca²⁺ ratio in early Cretaceous ‘calcite seas’, relative to modern oceans. Scapa cement compositions concur with published models in suggesting that Hauterivian ocean water had a Mg²⁺/Ca²⁺ ratio of ≤1. This is also supported by consideration of the spatial distribution of early calcite cement in terms of concretion growth kinetics. In contrast to the dominant early cement, late-stage ferroan, ¹⁸O-depleted calcites were sourced outwith the Scapa Member and precipitated after 1–2 km of burial. Our results emphasize that bioclast dissolution and low-Mg calcite cementation in sandstone reservoirs should not automatically be regarded as evidence for uplift and meteoric diagenesis.     

川北地区下寒武统筇竹寺组钙质结核特征及成因机制

不同成因的钙质结核在研究沉积水体、早期成岩环境及泥页岩的压实程度方面具有重要意义。通过对川北地区旺苍县下寒武统筇竹寺组钙质结核抛光,发现结核内部具有层理、暗色圈层和张裂缝构造。结核和围岩的层理关系和具有漂浮状的微观结构特征表明,该地区结核是形成于压实作用之前的成岩早期结核。对结核中Al、Ti、Ca、K、Na元素分析表明,结核的元素分布受到结核内部裂缝的影响。结核内部富含生物碎屑和其形成深度为数十米的特征,推测结核主要是在硫酸盐还原带生长。结核具有暗色圈层之间层理不弯曲和元素移动的特征,揭示了结核为透入性生长,在整个结核生长阶段就开始大量同时结晶。Mg/Ca和Sr/Ca的比值说明,结核内部钙质成分为富镁方解石-生物成因方解石。结核中富含钙质成分的原因可能是围岩中的生物成因方解石大量向结核运移所致。裂缝的形态特征表明,裂缝为张裂缝。对结核上部地层的沉积特征研究表明,张裂缝的成因很可能与筇竹寺顶部的浊积岩和沧浪铺组底部的似瘤状灰岩快速搬运沉积有关。     

Spherical and columnar, septarian, 18O-depleted, calcite concretions from Middle–Upper Permian lacustrine siltstones in northern Mozambique: evidence for very early diagenesis and multiple fluids

Calcite septarian concretions from the Permian Beaufort Group in the Maniamba Graben (NW Mozambique) allow controls on the composition and nature of diagenetic fluids to be investigated. The concretions formed in lacustrine siltstones, where they occur in spherical (1 to 70 cm in diameter) and columnar (up to 50 cm long) forms within three closely spaced, discrete beds totalling 2·5 m in thickness. Cementation began at an early stage of diagenesis and entrapped non‐compacted burrows and calcified plant roots. The cylindrical concretions overgrew calcified vertical plant roots, which experienced shrinkage cracking after entrapment. Two generations of concretionary body cement and two generations of septarian crack infill are distinguished. The early generation in both cases is a low‐Mn, Mg‐rich calcite, whereas the later generation is a low‐Mg, Mn‐rich calcite. The change in chemistry is broadly consistent with a time (burial)‐related transition from oxic to sub‐oxic/anoxic conditions close to the sediment–water interface. Geochemical features of all types of cement were controlled by the sulphate‐poor environment and by the absence of bacterial sulphate reduction. All types of cement present have δ¹³C ranging between 0‰ and −15‰(Vienna Peedee Belemnite, V‐PDB), and highly variable and highly depleted δ¹⁸O (down to 14‰ Vienna Standard Mean Ocean Water, V‐SMOW). The late generation of cement is most depleted in both ¹³C and ¹⁸O. The geochemical and isotopic patterns are best explained by interaction between surface oxic waters, pore waters and underground, ¹⁸O‐depleted, reducing, ice‐meltwaters accumulated in the underlying coal‐bearing sediments during the Permian deglaciation. The invariant δ¹³C distribution across core‐to‐rim transects for each individual concretion is consistent with rapid lithification and involvement of a limited range of carbon sources derived via oxidation of buried plant material and from dissolved clastic carbonates. Syneresis of the cement during an advanced stage of lithification at early diagenesis is considered to be the cause of development of the septarian cracks. After cracking, the concretions retained a small volume of porosity, allowing infiltration of anoxic, Ba‐bearing fluids, resulting in the formation of barite. The results obtained contribute to a better understanding of diagenetic processes at the shallow burial depths occurring in rift‐bound, lacustrine depositional systems.     

Effect of climate change on delivery and degradation of lipid biomarkers in a Holocene peat sequence in the Eastern European Russian Arctic

Lipid biomarkers from a peat plateau profile from the Northeast European Russian Arctic were analyzed. The peat originated as a wet fen ca. 9 ka BP and developed into a peat bog after the onset of permafrost ca. 2.5 ka BP. The distributions and abundances of n-alkanols, n-alkanoic acids, n-alkanes, n-alkan-2-ones and sterols were determined to study the effect of degradation on their paleoclimate proxy information. Plant macrofossil analysis was also used in combination with the lipid distributions. The n-alkanol and n-alkanoic acid distributions in the upper part of the sequence generally correspond to compositions expected from plant macrofossil assemblages. Their carbon preference index (CPI) values increase with depth and age, whereas those of the n-alkanes decrease. The different CPI patterns suggest that n-alkanoic acids and n-alkanols deeper in the sequence may be produced during humification through alteration of other lipids. Excursions in the n-alkanoic acid content also suggest an important contribution of invasive roots to the lipid biomarker composition. The CPIs associated with these compounds show that under permafrost conditions organic material from Sphagnum is better preserved than material from vascular plants. Increasing stanol/stenol ratio values and decreasing n-alkane CPI values indicate progressive degradation of organic matter (OM) with depth. The n-alkan-2-one/n-alkane and n-alkan-2-one/n-alkanoic acid ratios were shown to be useful proxies that can reflect the degree of OM preservation and suggest that both microbial oxidation of n-alkanes and decarboxylation of n-alkanoic acids produce n-alkan-2-ones in this peat sequence.     

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.     

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.     

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.     

Lipid,sterol and saccharide sources and dynamics in surface soils during an annual cycle in a temperate climate region

Multi-biomarkers were characterized in surface soils with different vegetation during an annual cycle in Oregon, U.S.A., to study the composition and dynamics of soil organic matter (SOM). The major compound classes identified include saccharides, steroids, terpenoids, and homologous series of aliphatic lipids (n-alkanoic acids, n-alkanols, and n-alkanes). Saccharides, n-alkanoic acids, and sterols were the most dominant compound groups identified in Ryegrass field soils, whereas n-alkanoic acids, n-alkanols, and sterols were dominant in soils under conifer and deciduous vegetation. Plant species, instead of microbial organisms, was found to be the primary source influencing the concentration and distribution of the major biomarker tracers in the studied surface soils. Over an annual cycle, concentrations of higher plant lipids such as monoacyl glycerides, sterols, n-alkanoic acids and total wax were higher during summer (especially June–August). During fall into winter, the concentrations of all compounds decreased to steady state levels due to cessation of de novo synthesis and concomitant biodegradation and remineralization of detritus. Sucrose and glucose reached maximum concentrations during spring (especially March–May), which could be related with plant growth, especially rootlets in the soils. Mycose, the microbial/fungal metabolite, maximized during late summer, suggesting the concomitant increase of microbial/fungal activity with the increasing primary production. The composition and variation of biomarkers observed over an annual cycle improved our understanding of SOM dynamics in temperate soils, which could also be linked to regional and global carbon cycles.