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.     

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.     

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.     

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 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.     

Geochemistry of the Hepworth Carboniferous sediment sequence and origin of the diagenetic iron minerals and concretions

The major element geochemistry of a mudstone sequence of Westphalian age has been studied in detail and mineralogical distributions calculated. Quartz and zircon trends indicate the energy of the depositional environment and this is closely reflected in the clay mineralogical composition. Of the detrital clays kaolinite is concentrated in the finer-grained sediments relative to illite. Chlorite and interstratified illite-smectite probably underwent diagenetic modification and small amounts of authigenic clays may have formed.Siderite, which occurs in both concretionary and disseminated form, and pyrite developed during diagenesis under reducing conditions and account for most of the iron present. Pyrite grew first deriving its iron partly from detrital clays. Carbon isotopic evidence suggests that early siderite precipitated in pore space as nodules and later in dispersed form. A second concretionary phase, pistomesite, grew during late dewatering. Siderite iron was derived mainly from Mn-rich oxidate phases.Titanium occurs as anatase uniformly distributed through the sequence. Phosphorus is mainly in diagenetic apatite and the $\text{sodium}\text{potassium}$ ratio is controlled by the micas. Adsorbed water is closely related to grain size and clay content.     

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.     

Petrography, chemistry and origin of early diagenetic concretions in the Lower Carboniferous of the Isle of Man

Three silicified limestone horizons of D1 age from the Visean of the Isle of Man contain calcitic concretions with peripheral silica crusts, occasionally surrounded by a further calcitic layer. Components of the original sediment include carbonate skeletons, carbonaceous grains, sponge spicules and muscovite. Diagenetic products include calcite, dolomite, pyrite, sphalerite, clays, feldspar and quartz. The concretions are composed of neomorphic calcite. The time of recrystallization and the identity of the neomorphic precurosor are both unknown. Displacive, fibrous calcite is chemically similar to neomorphic calcite and both are of early diagenetic age. Granular and rhombic ferroan calcites are of late diagenetic age and were precipitated from pore-waters with Sr/Ca, Mg/Ca and Fe/Ca ratios unlike those of seawater. The difference between early silicification which produced silica crusts and later diffuse silicification of the host sediment is related to a change in sediment transmissivity between the two silicification periods. A four-fold scheme of concretionary growth is proposed. The supply of silica is from sponge spicules and that of carbonate from seawater via porewater. The distribution of organic matter, either as sporadic large carcasses or as small carcasses concentrated in particular horizons, is believed to be vital for carbonate precipitation and controls the distribution of concretions. Awareness of the multiplicity of diagenetic changes is essential in interpretation of early porewater systems and in the origin of products which are often metastable and destined to subsequent changes. No single model is an explanation for all types of concretionary growth.     

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.     

Rinded iron‐oxide concretions: hallmarks of altered siderite masses of both early and late diagenetic origin

Iron‐bearing concretions are valuable records of oxidation states of subsurface waters, but the first concretions to form can be altered drastically during later diagenetic events. Distinctive concretions composed of heavy rinds of iron oxide that surround iron‐poor, mud‐rich cores are common along bases of fluvial cross‐bed sets of the Cretaceous Dakota Formation, Nebraska, USA. Concretion rinds thicken inward and cores contain 46 to 89% void space. Millimetre‐scale spherosiderites are abundant in palaeosols that developed in floodplain facies. Evolution of rinded concretions began when intraformational clasts were eroded from sideritic soils, transported, abraded and deposited in river channels. Alteration of siderite and formation of rinds occurred much later, perhaps in the Quaternary when sandstone pore waters became oxic. Dakota concretions are analogous to ‘rattlestones’ in Pleistocene fluvial channels of The Netherlands, and their rinded structure is analogous to that of iron‐rich concretions in the aeolian Navajo Sandstone of Utah. In all three deposits, rinded concretions formed when pre‐existing, siderite‐cemented concretions were oxidized within a sand matrix. Unlike fluvial examples, siderite in the Navajo Sandstone was autochthonous and of late diagenetic origin, having precipitated from carbon dioxide and methane‐enriched waters moving through folded and jointed strata. Iron‐rich rinds formed in all these strata because concretion interiors remained anaerobic, even as oxygen accumulated in the pore waters of their surrounding, permeable matrix. Iron oxide first precipitated at redox boundaries at concretion perimeters and formed an inward‐thickening rind. Acid generated by the oxidation reaction drove siderite dissolution to completion, creating the iron‐poor core. Iron‐oxide rinds are indicators of the former presence of siderite, a mineral that forms only under reducing conditions, during either early or late diagenesis. Siderite is vulnerable to complete oxidation upon exposure, so the distinctive rinded concretions are valuable clues that aid in deciphering diagenetic histories and for recognizing methanic floodplain palaeoenvironments and wet palaeoclimate.     

CO2 emission accompanying the fracture of calcite

Time resolved mass spectroscopy of the emissions accompanying the fracture of calcite (rhombohedral CaCO₃) show that the principle volatile product, CO₂, is released in bursts milliseconds after the fracture event. Similar measurements during the abrasion of calcite and during low temperature thermal decomposition of pulverized calcite show similar CO₂ bursts. We argue that the observed bursts reflect localized decomposition of the calcite during the relaxation of reversible plastic deformation created by fracture and abrasion. This implies that mechanical, non-thermal processes play an important role in producing the observed decomposition products.     

Interpreting fracture development from diagenetic mineralogy and thermoelastic contraction modeling

Four sets of thin-section scale, Mode I (open mode), cemented microfractures are present in sandstone from the Eocene Misoa Formation, Maracaibo basin, Venezuela. The first set of microfractures is intragranular (F1), formed early during compaction and are filled with quartz cement precipitated at temperatures equal to or higher than 100 °C. The second set of microfractures (F2) is cemented by bituminite–pyrite, formed at temperatures between 60 and 100 °C, and are associated with kerogen maturation and hydrocarbon migration from underlying overpressured source rocks. The third set of microfractures (F3) is fully cemented by either quartz cement or calcite cement. The former has fluid inclusion homogenization temperatures between 149 and 175 °C. These temperatures are mostly higher than maximum burial temperatures (160 °C), suggesting that upward flow, caused by a pressure gradient, transported silica vertically which crystallized into the fractures. Upward decompression may have also caused a P_CO2 drop, which, at constant temperature, allowed simultaneous carbonate precipitation into the third microfracture set. The fourth set of thin-section scale microfractures (F4) is open or partially cemented by siderite–hematite and other iron oxides. The presence of hematite and iron oxides in microfractures is evidence for oxidizing conditions that may be associated with the uplift of the Misoa formation. In order to time and place constraints on the depth of formation of the fourth set of microfractures, we have coupled published quartz cementation kinetic algorithms with uniaxial strain equations and determined if, in fact, they could be associated with the uplift of the formation. Our results suggest that thermoelastic contraction, caused by the formation's uplift, erosion, and consequent cooling is a feasible mechanism for the origin of the last fracture set. Hence, we infer that meteoric water invasion into the fractures, at the end of the uplift, cause the precipitation of oxides and the transformation of siderite to hematite.     

Fatty acids in fossil fruits

Fatty acids extracted from six fruit of Nyssa fissilis from the Early Tertiary Brandon Lignite, Vermont, include mainly palmitic, palmitoleic, stearic, and oleic acids and a number of probable branched chain acids. Four unidentified ‘round fruit’ from the lignite contained the same acids in predominance. The two taxa were chemically indistinguishable because of wide intraspecific variation in percentage of each n-fatty acid present. ‘Fingerprint’ chromatograms of non-aromatic hydrocarbon extracts from two distinct taxa of fruit from an Eocene clay of Tennessee also showed no consistent interspecific differences. We conclude that degradation and removal of the seed food reserves and introduction of extraneous lipids limits the utility of fatty acids and hydrocarbons in chemosystematic study of fossil fruits at the species and genus levels.     

Microscopic calcite dendrites in cold-water tufa: implications for nucleation of micrite and cement

Dendritic calcite forms in an active cold-water tufa system in association with extracellular polymeric substances (EPS) that discontinuously coat bryophytes and cyanobacteria. Dendrites consist of 100–200 nm thick calcite fibres that form 3D lattice-like domains. In each dendrite domain, fibres have three structurally equal orientations, which correspond in disposition to radii from the centre of a calcite unit cell to the convex triple face junctions on its surface. Fibres do not form in the orientation of the c-axis. The external form of each dendrite has the shape of half of a shortened octahedron, with an upper triangular surface parallel to the substrate. Dendrite nucleation takes place on or in microbial EPS, whether microbial cells are present or not, and is probably effected by attraction of Ca²⁺ cations to negatively charged EPS, together with CO₂-degassing and concomitant pH increase of supersaturated spring water in stream splash zones. Ensuing dendrite growth is abiogenic and controlled by diffusion. Dendrite c-axes are perpendicular to the substrate, probably because the negative charge of EPS forces the orientation of Ca²⁺ and CO planes within the developing dendrite crystal to be parallel to the EPS film surface. Dendrites are eventually filled and overgrown by solid, syntaxial calcite, which gradually and completely obliterates the dendrites as more familiar calcite crystal forms develop. No trace of the dendritic nucleus remains in the rock record. Calcite crystal nucleation may take place by this mechanism in many marine and meteoric settings, given that microbial EPS is now assumed to be virtually ubiquitous in these environments. This phenomenon could contribute to the development of familiar fabrics such as marine micrite cement and fibrous calcite cement, radial ooids, peloids, ‘abiogenic’ stromatolites, sea floor precipitates, microbialites, tufa, travertine, speleothems, and some meteoric cements. It may also contribute to the substrate-normal orientation of c-axes of common cement fabrics.     

Radiaxial fibrous calcites as low-magnesian calcite cement precipitated in a marine-meteoric mixing zone

Abstract Radiaxial fibrous calcite (RFC) has previously been interpreted as a marine or replacive cement. Study of the Dongjeom Formation (Early Ordovician), Korea, shows that RFC can form in marine‐meteoric mixing zones as a low‐magnesian calcite (LMC) cement. RFC in the shallow‐marine Dongjeom Formation occurs in arenaceous limestones at the top of a transgressive facies overlying a regressive facies. It shows well‐developed growth zonation, and lighter oxygen isotope values and more radiogenic strontium isotope ratios than those of Early Ordovician marine calcite. Such petrographic and chemical evidence indicates that the RFC was precipitated as a primary LMC cement in a marine and meteoric mixing zone. Owing to the unique environment of formation, the Dongjeom RFC is characterized by growth zonal fabric comprising alternating subzones, which may indicate precipitation from varying fluids. In addition, this study documents the importance of substrate for development of RFC. Early ‘nucleation’ for RFC occurred mainly on microcrystalline skeletal grains and internal sediments, whereas on homogeneously altered substrates, thin‐coated banding structure developed, ultimately forming coarse crystalline spar. This suggests that microcrystalline substrates are preferred sites for nucleation of RFC.     

The diagenetic production of α-keto acids in heated and fossil Chione shells

Both pyruvic and α-ketobutyric acids are formed during heating experiments with modern Chione shells. These α-keto acids are also present in fossil specimens. These findings provide additional evidence that the dehydration reaction of free serine and threonine or the β-elimination reaction of peptide bound serine and threonine occurred in fossil materials. These experiments suggest that the formation of α-keto acids occurs early in protein diagenesis. A large fraction of the α-keto acids which were formed have been lost either by subsequent reactions or by diffusion out of the shell matrix.     

Fatty acids and hydrocarbons in surficial sediments of Lake Huron

Fatty acid and hydrocarbon distributions in surficial sediments from ten locations in southern Lake Huron indicate both aquatic and terrigenous recent biological sources of these geolipid materials. Normal alkanoic acids appear to be derived primarily from aquatic sources whereas normal alkanes are from multiple origins. Geolipid distributions are determined by the nature of the biogenic source and are modified during transport and deposition. Sediments receiving urban runoff in Saginaw Bay contain large amounts of non-biogenic hydrocarbons of a petroleum or industrial nature.     

Fatty acids of bacterial origin in contemporary marine sediments

Contributions by bacteria to recent sediments have been recognized as one important source of input for the extractable lipids. It has, however, proved difficult so far to conclusively relate the components identified to the contributing bacteria. This fact is primarily related to the lack of information on both the lipid chemistry of marine bacteria, and of detailed structures of the sedimentary lipids. In this paper a study of the fatty acids from a tropical marine sediment selected because of its high biomass content is reported, and relationships between the sedimentary extracts of the surface layer to fatty acid components of bacteria cultured from the sediment sample are detailed. By selecting specific structural features, a group of fatty acids have been identified as valid markers for bacteria in this environment: these include iso- and anteiso-branched chain acids; 10-methylpalmitic acid; cyclopropyl 17:0 and 19:0 acids of which ▽19:0 (11,12) is unique to bacteria; cis-vaccenic acid; and the 15:1, 17:1 ω6 and ω8 isomers especially when these occur in pairs; iso Δ7–15: 1 and iso Δ9–17:1 are branched unsaturated acids apparently unique to bacteria. Trans-monoene fatty acids are likely to be a direct bacterial input, and the hydroxy acids identified are probably of bacterial cell wall origin. This study, whilst emphasizing the necessity for detailed structural information on fatty acids in order to use them validly as biological markers, considerably extends the range of fatty acids as markers of bacterial input to contemporary sediments.