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.     

Coupled uranium mineralisation and bacterial sulphate reduction for the genesis of the Baxingtu sandstone-hosted U deposit,SW Songliao Basin,NE China

The Baxingtu deposit is a typical redox front tabular-shaped uranium deposit hosted in sandstones of the Late Cretaceous Yaojia Formation deposited within a braided river environment during the post-rift stage of the Songliao Basin, in northeast China. This study proposes the first metallogenic model for the Baxingtu deposit and provides new data on genetic processes involved in the uranium mineralisation of sandstone-type deposits that were characterised through petrographic observations, whole-rock geochemistry, and geochemical and/or mineralogical study of iron disulphide, uranium minerals, Fe-Ti oxides (EPMA, LA-ICP-MS), and organic matter (REP). The δ³⁴S value has been measured in situ by SIMS on the different generations of iron disulphide.Within regional primary reduced sandstones, pre-ore uranium enrichment (U_mean = 7.6 ppm in whole rock) was identified on altered Fe-Ti oxides along with minor concentrations on organic matter (respectively 26.3% and 1.3% of the whole-rock U content), which together represent a significant source of uranium for the mineralisation. Additional pre-ore uranium concentrations may also be associated with clay minerals. Petrographic observations and REP data indicate that organic matter occurring in the host-sandstone is mainly inherited from land plants and corresponds to type III or type IV kerogens. Ore-stage iron disulphides largely occur as framboids and in replacement of organic matter or also as sub-idiomorphic to idiomorphic cement and crystal. Trace element signatures detected within framboids are likely indicative of formation mainly from a single event. Framboids and iron disulphide in replacement of organic matter have a light sulphur isotope signature characterised by δ³⁴S values from −72.0 to −6.2‰, suggesting that sulphur originated from bacterial sulphate reduction, which was mainly responsible for (1) the liberation of U from Fe-Ti oxides and organic matter, (2) the generation of ore-stage iron disulphides, (3) the bioreduction of uranium and (4) the production of a secondary H₂S-rich reducing barrier also involved in uranium reduction. Uranyl and sulphate ions were transported through the host sandstone by low-temperature oxygenated groundwater and U(IV) was precipitated at the redox interface as nano to microcrystals of pitchblende and coffinite, dominantly associated with bacterial substrate and as intergrowth with biogenic iron disulphide or directly associated with organic matter and residual Ti-Fe oxides. The uranium mineralisation does not replace ore-stage iron disulphides. Therefore, the combined mineralogical, geochemical, and isotopic characteristics of the Baxingtu tabular uranium deposit characterise dominantly biogenic processes for the genesis of the uranium mineralisation.     

Thermochemical sulphate reduction in the Upper Devonian Cairn Formation of the Fairholme carbonate complex (South-West Alberta, Canadian Rockies): evidence from fluid inclusions and isotopic data

The Fairholme carbonate complex is part of the extensively dolomitized Upper Devonian carbonate reefs in west-central Alberta. The studied formations contain moulds (up to 10 cm in diameter), which are filled partially with (saddle) dolomite, quartz and calcite cements. These cements precipitated from a mixture of brines that acquired high salinity by dissolution of halite and brines derived from evaporated sea water. The fluids were warm (homogenization temperature of primary fluid inclusions of 76 to 200 °C) and saline (20 to 25 wt% NaCl equivalent) and testify to thermochemical sulphate reduction processes. The latter is deduced from S in solid inclusions, CO₂ and H₂S in volatile-rich aqueous inclusions and depleted δ¹³C values down to −26‰ Vienna Pee Dee Belemnite. High ⁸⁷Sr/⁸⁶Sr values (0·7094 to 0·7110) of the cements also indicate interaction of the fluids with siliciclastic sequences. The thermochemical sulphate reduction-related cements probably formed during early Laramide burial. Another (younger) calcite phase, characterized by depleted δ¹⁸O values (−23·9‰ to −13·9‰ Vienna Pee Dee Belemnite), low Na (27 to 37 p.p.m.) and Sr (39 to 150 p.p.m.) concentrations and non-saline (∼0 wt% NaCl equivalent) fluid inclusions, is attributed to post-Laramide meteoric water.     

Silicification of sulphate evaporites and their carbonate replacements in Eocene marine sediments, Tunisia: two diagenetic trends

Samples of chert nodules, diagenetic carbonates and evaporites (gypsum/anhydrite) collected from the gypsiferous limestones of the Kef Eddour Member (Ypressian‐Priabonian) near Metlaoui and Sehib (Tunisia) show selective silicification with great variety in the silicified by‐products. Based on δ¹³C values, which support an organic origin for the carbon, carbonates replaced evaporites microbially through bacterial sulphate reduction. Observations and results suggest two scenarios for chert formation that are related to the rate and timing of diagenetic carbonate replacement of the evaporites (anhydrite/gypsum). In the absence of early diagenetic carbonate phases, silica with δ¹⁸O values from +25 to +28·6‰ [standard mean ocean water (SMOW)] replaced the outer parts of anhydrite nodules at pH < 9. In contrast, pore‐fluid pH values > 9 in the innermost parts of the anhydrite nodules prevented silica precipitation. The record of this chemical barrier is preserved in the microquartz rims and geode features that formed in the inner parts of the nodules after dissolution of the anhydrite nucleus. The microbial diagenetic replacement of evaporites (bacterial sulphate reduction) by carbonates (calcite, aragonite and dolomite) favoured silica replacement of carbonates rather than evaporites. Silica, with δ¹⁸O signature of +21 to +26‰ (SMOW), replaced carbonates on a volume‐for‐volume basis, yielding a more siliceous groundmass, and accounting for 90–95% of the nodules. The relatively higher δ¹⁸O values of quartz replacing anhydrite can be explained by a diagenetic fluid in equilibrium with mixed (meteoric/marine) to marine water. The lower δ¹⁸O values of the quartz that replaced the diagenetic carbonates are ascribed to flushing by meteoric water in a later diagenetic stage. The silica supply for chert formation could be derived from the reworked bio‐siliceous deposits (diatomites) to the west of the basin [vestiges of an opal‐CT precursor undetectable by X‐ray diffraction (XRD) were revealed by δ²⁹Si magic‐angle‐spinning nuclear magnetic resonance investigations], diagenesis of the extraformational and overlying clay‐rich beds (the host limestones are clay‐poor as shown by XRD measurements), and minor volcanogenic and hydrothermal contributions during early diagenetic stages.     

Paragenesis of Cretaceous to Eocene carbonate reservoirs in the Ionian fold and thrust belt (Albania): relation between tectonism and fluid flow

ABSTRACT This paper examines the diagenetic history of dual (i.e. matrix and fracture) porosity reservoir lithologies in Cretaceous to Eocene carbonate turbidites of the Ionian fold and thrust belt, close to the oil‐producing centre of Fier–Ballsh (central Albania). The first major diagenetic event controlling reservoir quality was early cementation by isopachous and syntaxial low‐Mg calcite. These cements formed primarily around crinoid and rudist fragments, which acted as nucleation sites. In sediments in which these bioclasts are the major rock constituent, this cement can make up 30% of the rock volume, resulting in low effective porosity. In strata in which these bioclasts are mixed with reworkedmicrite, isopachous/syntaxial cements stabilized the framework, and matrixporosity is around 15%. The volumetric importance of these cements, their optical and luminescence character (distribution and dull orange luminescence) and stable isotopic signal (δ¹⁸O and δ¹³C averaging respectively; ?0·5‰ VPDB and +2‰ VPDB) all support a marine phreatic origin. Within these turbidites and debris flows, several generations of fractures alternated with episodes of cementation. A detailed reconstruction of this history was based on cross‐cutting relationships of fractures and compactional and layer‐parallel shortening (LPS) stylolites. The prefolding calcite veins possess orange cathodoluminescence similar to that of the host rock. Their stable isotope signatures (δ¹⁸O of ?3·86 to ?0·85‰ VPDB and δ¹³C of – 0·14 to + 2·98‰ VPDB) support a closed diagenetic rock‐buffered system. A similar closed system accounts for the selectively reopened and subsequently calcite‐cemented LPS stylolites (δ¹⁸O of ?1·81 to ?1·14‰ VPDB and δ¹³C of +1·52 to +2·56‰ VPDB). Within the prefolding veins, brecciated host rock fragments and complex textures such as crack and seal features resulted from hydraulic fracturing. They reflect expulsion of overpressured fluids within the footwall of the frontal thrusts. After folding and thrust sheet emplacement, some calcite veins are still rock buffered (δ¹⁸O of ?0·96 to +0·2‰ VPDB and δ¹³C of +0·79 to +1·37‰ VPDB), whereas others reflect external (i.e. extraformational) and thus large‐scale fluid fluxes. Some of these veins are linked to basement‐derived fluid circulation or originated from fluid flow along evaporitic décollement horizons (δ¹⁸O around +3·0‰ VPDB and δ¹³C around +1·5‰ VPDB). Others are related to the maturation of hydrocarbons in the system (δ¹⁸O around ?7·1‰ VPDB and δ¹³C around +9·3‰ VPDB). An open joint system reflecting an extensional stress regime developed during or after the final folding stage. This joint system enhanced vertical connectivity. This open joint network can be explained by the high palaeotopographical position and the folding of the reservoir analogue within the deformational front. The joint system is pre‐Burdigalian in age based upon a dated karstified discordance contact. Sediment‐filled karst cavity development is linked to meteoric water infiltration during emergence of some of the structures. Despite its sediment fill, the karst network is locally an important contributor to reservoir matrix porosity in otherwise tight lithologies. Development of secondary porosity along bed‐parallel and bed‐perpendicular (i.e. layer‐parallel shortening) stylolites is interpreted as a late‐stage diagenetic event associated with migration of acidic fluids during hydrocarbon maturation. Development of porosity along the LPS system enhanced the vertical reservoir connectivity.     

Deep‐burial alteration of early‐diagenetic carbonate concretions formed in Palaeozoic deep‐marine greywackes and mudstones (Bardo Unit,Sudetes Mountains,Poland)

Carbonate concretions formed in bathyal and deeper settings have been studied less frequently than those formed in shallow‐marine deposits. Similarly, concretions affected by catagenetic conditions have rarely been reported. Calcite concretions in deep‐marine mudstones and greywackes of the Bardo Unit (Sudetes Mountains, Poland) formed during early diagenesis and were buried to significant depths. Petrographic and geochemical (elemental and stable C and O isotopic) analyses document their formation close to the sediment–water interface, prior to mechanical compaction within the sulphate reduction zone and their later burial below the oil window. Although the concretions were fully formed during early diagenesis, the effects of increased temperature and interaction with late‐diagenetic interstitial fluids can be discerned. During maximum burial, the concretions underwent thorough recrystallization that caused alteration of fabric and elemental and O isotope composition. The initial finely crystalline cement was replaced by more coarsely crystalline, sheaf‐like, poikilotopic calcite in the concretions. These large calcite crystals engulf and partially replace unstable detrital constituents. The extremely low δ¹⁸O values (down to ?21·2‰ Vienna Pee Dee Belemnite) in the concretions are the result of the increased temperature in combination with alteration of volcanic glass, both causing a significant ¹⁸O‐depletion of bicarbonate dissolved in the interstitial fluids. Recrystallization led to uniform O isotope ratios in the concretions, but did not affect the C isotope signature. The δ¹³C values of the late‐diagenetic cements precipitated in the greywacke and in cracks cutting through concretions imply crystallization in the catagenetic zone and decarboxylation as a source of the bicarbonate. These late‐diagenetic processes took place in a supposedly overpressured setting, as suggested by clastic dykes and hydrofractures that cut through both concretions and host rock. All of these features show how the effects of early and late diagenesis can be distinguished in such rocks.     

Petrographic and geochemical evidence for the formation of primary, bacterially induced lacustrine dolomite: La Roda 'white earth' (Pliocene, central Spain)

Upper Pliocene dolomites (‘white earth’) from La Roda, Spain, offer a good opportunity to evaluate the process of dolomite formation in lakes. The relatively young nature of the deposits could allow a link between dolomites precipitated in modern lake systems and those present in older lacustrine formations. The La Roda Mg‐carbonates (dolomite unit) occur as a 3·5‐ to 4‐m‐thick package of poorly indurated, white, massive dolomite beds with interbedded thin deposits of porous carbonate displaying root and desiccation traces as well as local lenticular gypsum moulds. The massive dolomite beds consist mainly of loosely packed 1‐ to 2‐μm‐sized aggregates of dolomite crystals exhibiting poorly developed faces, which usually results in a subrounded morphology of the crystals. Minute rhombs of dolomite are sparse within the aggregates. Both knobbly textures and clumps of spherical bodies covering the crystal surfaces indicate that bacteria were involved in the formation of the dolomites. In addition, aggregates of euhedral dolomite crystals are usually present in some more clayey (sepiolite) interbeds. The thin porous carbonate (mostly dolomite) beds exhibit both euhedral and subrounded, bacterially induced dolomite crystals. The carbonate is mainly Ca‐dolomite (51–54 mol% CaCO₃), showing a low degree of ordering (degree of ordering ranges from 0·27 to 0·48). Calcite is present as a subordinate mineral in some samples. Sr, Mn and Fe contents show very low correlation coefficients with Mg/Ca ratios, whereas SiO₂ and K contents are highly correlated. δ¹⁸O‐ and δ¹³C‐values in dolomites range from ?3·07‰ to 5·40‰ PDB (mean=0·06, σ=1·75) and from ?6·34‰ to ?0·39‰ PDB (mean=?3·55, σ=1·33) respectively. Samples containing significant amounts of both dolomite and calcite do not in general show significant enrichment or depletion in ¹⁸O and ¹³C between the two minerals. The correlation coefficient between δ¹⁸O and δ¹³C for dolomite is extremely low and negative (r=?0·05), whereas it is higher and positive (r=0·47) for calcite. The lacustrine dolomite deposit from La Roda is interpreted mainly as a result of primary precipitation of dolomite in a shallow, hydrologically closed perennial lake. The lake was supplied by highly saturated HCO₃^?/CO₃^2? groundwater that leached dolomitic Mesozoic formations. Precipitation of dolomite from alkaline lake waters took place under a semi‐arid to arid climate. However, according to our isotopic data, strong evaporative conditions were not required for the formation of the La Roda dolomite. A significant contribution by bacteria to the formation of the dolomites is assumed in view of both petrographic and geochemical evidence.     

C, O, S and Sr isotope studies on the genesis of Fe-carbonate and barite mineralizations in the Attepe iron district (Adana, Southern Turkey)

The Attepe district consists of Precambrian, Lower–Middle Cambrian, Upper Cambrian–Lower Ordovician and Mesozoic formations. It contains several iron deposits and occurrences. Three types of iron-mineralizations can be distinguished in the area; (i) Sedimentary Fe-sulfide in Precambrian bituminous metapelitic rocks, and Fe-oxides in Precambrian metasandstones (SISO), (ii) vein-type Fe-carbonate and oxides composed of mainly siderite, ankerite and hematite including barite in Lower–Middle Cambrian metacarbonates of the Çaltepe Formation (HICO), (iii) karstic Fe-oxides and hydroxides essentially in the Lower–Middle Cambrian metacarbonates and the unweathered Fe-carbonates (KIO). The latter type is more widespread and located at the upper parts of the most important mineable iron deposits like Attepe deposit.

Oxygen-, carbon-, sulfur- and strontium-isotope studies have been performed on siderites and barites in the vein-type ores, and on calcites in the recrystallized Çaltepe Limestones to investigate the sources and formation mechanism of primary ore-forming constituents. The δ¹³C values of siderites and calcites in limestones of the Çaltepe Formation range from −10.10‰ to −8.20‰, and from −0.8‰ to 2.30‰. Both carbonate minerals show δ¹⁸O values between 17.50–18.30‰ and 16.20–23.00‰, respectively. The δ¹³C and δ¹⁸O isotopic variations do not indicate any direct or linear relations between siderites and limestones. However, it is possible that the carbon and oxygen isotopic compositions of carbonate minerals could be changed to some extent, when limestones were subjected to hydrothermal processes or thermal alterations during metamorphism.

The isotopic values of barites display 32.40–38.30‰ for δ³⁴S and 12.20–14.70‰ for δ¹⁸O. The strontium isotope ratios (0.717169–0.718601) of barites and the sulfur isotope compositions of barites and pyrites suggest that there are no direct linkages of ore-forming compounds neither with a magmatic source nor with sedimentary pyrite formations in the Precambrian bituminous shales of the Attepe formation.

According to the field observations and the stable isotope data, siderites and ankerites should be formed by interaction between iron-rich hydrothermal fluids and Çaltepe limestones, whereas isotope ratios of barites indicate that they were formed by mixing of sulfur-rich meteoric waters and deeply circulated hydrothermal solutions.     

Water-rock-tailings interactions and sources of sulfur and metals in the subtropical mining region of Taxco,Guerrero (southern Mexico): A multi-isotopic approach

Multi-isotope (H, O, S, Sr, Pb) systems coupled with conventional (major and trace element) hydrogeochemical analysis were applied to determine the origin of water, to model water-rock-tailings interactions and for source apportionment of sulfur and associated toxic metals in the mining region of Taxco, Guerrero in southern Mexico. Oxygen and H isotopes indicate that meteoric water in the zone is rainwater undergoing varying degrees of isotopic fractionation by atmospheric evaporation whereas Sr isotopes trace the interaction of pristine water from volcanics of the regional recharge zone and subsequently flowing through sandstone and shale to spring points. Leachates form from two distinctive sources (spring water and surface water) having differential interactions with bedrocks prior to entering the tailings. Compared to pristine water, leachates are enriched in sulfate, metals (e.g. Fe, Mn, Pb and Zn) and metalloids (e.g. As). The sulfur isotopic composition of ore-sulfides, leachates, secondary precipitates, regional surface water and hypogenic sulfates is described in terms of a two-component mixing model with shale of Mexcala and limestone of Morelos formations representing the light and heavy end-members, respectively, whereas Sr isotopic composition is bracketed combining three lithogenic (Mexcala/Morelos, Tilzapotla and Taxco Schist) sources. Finally, leachates have a mixture of lead from ore-sulfides and Taxco Schist Formation (Family I) or from ore-sulfides alone (Family II). The application of multiple environmental isotopic techniques is an outstanding tool for elucidating complex interactions of water with bedrocks and tailings and for determining the source of sulfur and toxic metal from mining and other metal polluted environments.     

Palaeoenvironmental and diagenetic reconstruction of a closed‐lacustrine carbonate system – the challenging marginal setting of the Miocene Ries Crater Lake (Germany)

Chemostratigraphic studies on lacustrine sedimentary sequences provide essential insights on past cyclic climatic events, on their repetition and prediction through time. Diagenetic overprint of primary features often hinders the use of such studies for palaeoenvironmental reconstruction. Here the potential of integrated geochemical and petrographic methods is evaluated to record freshwater to saline oscillations within the ancient marginal lacustrine carbonates of the Miocene Ries Crater Lake (Germany). This area is critical because it represents the transition from shoreline to proximal domains of a hydrologically closed system, affected by recurrent emergent events, representing the boundaries of successive sedimentary cycles. Chemostratigraphy targets shifts related to subaerial exposure and/or climatic fluctuations. Methods combine facies changes with δ ¹³C–δ ¹⁸O chemostratigraphy from matrix carbonates across five closely spaced, temporally equivalent stratigraphic sections. Isotope composition of ostracod shells, gastropods and cements is provided for comparison. Cathodoluminescence and back‐scatter electron microscopy were performed to discriminate primary (syn‐)depositional, from secondary diagenetic features. Meteoric diagenesis is expressed by substantial early dissolution and dark blue luminescent sparry cements carrying negative δ ¹³C and δ ¹⁸O. Sedimentary cycles are not correlated by isotope chemostratigraphy. Both matrix δ ¹³C and δ ¹⁸O range from ca −7·5 to +4·0‰ and show clear positive covariance (R  = 0·97) whose nature differs from that of previous basin‐oriented studies on the lake: negative values are here unconnected to original freshwater lacustrine conditions but reflect extensive meteoric diagenesis, while positive values probably represent primary saline lake water chemistry. Noisy geochemical curves relate to heterogeneities in (primary) porosity, resulting in selective carbonate diagenesis. This study exemplifies that ancient lacustrine carbonates, despite extensive meteoric weathering, are able to retain key information for both palaeoenvironmental reconstruction and the understanding of diagenetic processes in relation to those primary conditions. Also, it emphasizes the limitation of chemostratigraphy in fossil carbonates, and specifically in settings that are sensitive for the preservation of primary environmental signals, such as lake margins prone to meteoric diagenesis.     

Host rock dolomitization and secondary porosity development in the Upper Devonian Cairn Formation of the Fairholme carbonate complex (South‐west Alberta,Canadian Rockies): diagenesis and geochemical modelling

The Upper Devonian carbonate reefs in West‐central Alberta are important petroleum reservoirs that are well‐known for their extensive secondary porosity. An outcrop analogue study indicates that an early matrix‐selective dolomitization event occurred which is characterized by a major Late Devonian sea water component with increased salinity because of evaporation. It is interpreted that the matrix (replacive) dolomite formed during the Famennian as the result of a combination of both seepage and latent reflux dolomitization, although an additional type or overprinting of later intermediate burial dolomitization cannot be excluded. Formation of the moulds is attributed mainly to the dissolution of undolomitized fossil cores, most typically stromatoporoids. Geochemical modelling indicates that carboxylic acid fluids have the highest potential for dissolving residual calcite in this case. Geochemical models consistent with this analysis and interpretations can reproduce the secondary porosity and suggest a viable dolomitization process for the localities studied.     

Facies analysis and correlation of high-order sequences in middle–outer ramp successions: variations in exported carbonate on basin-wide δ13Ccarb (Kimmeridgian, NE Spain)

Carbonate mud that accumulated in the deep parts of a late Kimmeridgian carbonate ramp (Iberian Basin, NE Spain) was partly derived by resedimentation from shallow water production areas. High-frequency sea-level changes, probably driven by climatic changes in tune with precession and short-eccentricity cycles, affected carbonate production and the amount of exported sediment. Facies analysis and correlation of three outcrops located in middle and outer ramp settings allows a comparison of high-order sequences (bundles of beds and sets of bundles) across a ramp transect and an assessment of the carbonate factory. Analysis of the storm deposits found in middle ramp settings identifies deepening to shallowing high-frequency cycles based on the level of exported carbonate. In outer ramp areas, many of the bundles exhibit a thinning trend, indicating a progressive decrease of carbonate production and hence, carbonate export during periods of high-frequency sea-level rise. δ¹³C_carb values show a gradual increase through the studied long-term transgressive interval ranging from 1·5‰ to 2·8‰. Within this long-term evolutionary trend, short-term δ¹³C_carb fluctuations occur that correspond with some of the high-order cycles defined from sedimentary facies analysis. These short-term δ¹³C_carb shifts are interpreted as shifts in carbonate export from shallow reef regions to the outer ramp. A consequence of this study is that variation in δ¹³C_carb can be used for correlation in outer ramp successions, at least on a basin-wide scale.