Dolomitization,gypsum calcitization and silicification in carbonate–evaporite shallow lacustrine deposits

This paper describes and interprets the mineral and facies assemblages that occur in carbonate–evaporite shallow lacustrine deposits, considering the importance of the processes pathway (i.e. dolomitization, gypsum calcitization and silicification). The Palaeogene deposits of the Deza Formation (Almazán Basin, central‐northern Spain) are selected as a case study to determine the variety of physicochemical processes taking place in carbonate–evaporite shallow lakes and their resulting diagenetic features. Dolostones are the predominant lithology and are composed mainly of dolomite with variable amounts of secondary calcite (5 to 50%), which mainly mimic lenticular gypsum (pseudomorphs). Five morphological types of dolomite crystal were identified as follows: dolomite tubes, dolomite cylinders, rhombohedral dolomite, spheroidal and quasi‐rhombohedral dolomite, and cocoon‐shaped dolomite. The dolomite cylinders and tubes are interpreted as the dolomitized cells of a widespread microbial community. The sequence of diagenetic processes started with growth of microlenticular interstitial gypsum in a calcareous mud deposited on the playa margin mudflats, and that sometimes included microbial sediments. Immediately following growth of gypsum, dolomite replaced the original calcite (or possibly aragonite) muds, the microbial community and the gypsum. Partial or total replacement of gypsum by dolomite was related mainly to the biomineralization of endolithic microbial communities on gypsum crystals. Later calcitization took place under vadose, subaerial exposure conditions. The development of calcrete in distal alluvial settings favoured the release of silica and subsequent silicification on the playa margin mudflats. Stable isotope compositions of calcite range from ?9·02 to ?5·83‰ δ¹³C_PDB and ?7·10 to 1·22‰ δ¹⁸O_PDB; for the dolomite, these values vary from ?8·93 to ?3·96‰ δ¹³C_PDB and ?5·53 to 2·4‰ δ¹⁸O_PDB. Quartz from the cherts has δ¹⁸O_SMOW values ranging from 27·1 to 31·1‰. Wide variation and relatively high δ¹⁸O_SMOW values for dolomite indicate evaporitic and closed hydrological conditions; increased influx of meteoric waters reigned during the formation of secondary calcite spar.     

Dolomitization of the Capitan Formation forereef facies (Permian, west Texas and New Mexico): seepage reflux revisited

Abstract Interpretation of seepage reflux dolomitization is commonly restricted to intervals containing evaporites even though several workers have modelled reflux of mesosaline brines. This study looked at the partially dolomitized forereef facies of the Capitan Formation to test the extent of reflux dolomitization and evaluate the possible role of the near‐backreef mesosaline carbonate lagoon as an alternative source of dolomitizing fluids. The Capitan Formation forereef facies ranges from 10% to 90% dolomite. Most of the dolomite is fabric preserving and formed during early burial after marine cementation, before and/or during evaporite cementation and before stylolitization. Within the forereef facies, dolomite follows depositional units, with debris‐flow and grain‐flow deposits the most dolomitized and turbidity‐current deposits the least. The amount of dolomite increases with stratigraphic age and decreases downslope. Within the reef facies, dolomite is restricted to haloes around fractures and primary cavities except where the reef facies lacks marine cements and, in contrast, is completely dolomitized. This dolomite distribution supports dolomitization by sinking fluids. Oxygen isotopic values for fabric‐preserving dolomite (δ¹⁸O = 0·9 ± 1·0‰, N = 101) support dolomitization by sea water to isotopically enriched sea water. These values are closer to the near‐backreef dolomite (δ¹⁸O = 2·1 ± 0·7‰, N = 48) than the hypersaline backreef dolomite (δ¹⁸O = 3·6 ± 0·9‰, N = 11). Therefore, the fabric‐preserving dolomite is consistent with dolomitization during seepage reflux of mainly mesosaline brines derived from the near‐backreef carbonate lagoon. The occurrence of mesosaline brine reflux in the Capitan Formation has important implications for dolomitization in forereef facies and elsewhere. First, any area with a restricted carbonate lagoon may be dolomitized by refluxing brines even if there are no evaporite facies present. Secondly, such brines may travel significant distances vertically provided permeable pathways (such as fractures) are present. Therefore, the absence of immediately overlying evaporite or restricted facies is not sufficient cause to eliminate reflux dolomitization from consideration.     

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.     

Diagenetic origin of Basal Anhydrite in the Cretaceous Maha Sarakham salt: Khorat Plateau, NE Thailand

Development of a diagenetic anhydrite bed at the base of the Cretaceous Maha Sarakham Saline Formation (the `Basal Anhydrite' member) of the Khorat Plateau in north-eastern Thailand took place due to leaching and/or pressure dissolution of salt at the contact between an underlying active sandstone aquifer system and an overlying massive halite-dominated evaporite sequence. Basal evaporites composed of halite with intercalated anhydrite of the latter sequence are undergoing dissolution as a result of subsurface flushing, with anhydrite produced as the insoluble residue. The result is a 1·1 m thick interval of nodular anhydrite displaying unique, basin-wide continuity. Observed textures, petrographic features and chemical data from the anhydrite and associated authigenic minerals support the origin of the Basal Anhydrite Member as an accumulation residue from the dissolution of the Maha Sarakham salts. Petrographically, the anhydrite in this unit is made up of crystals that are blocky and recrystallized, sheared, generally elongated and broken, and is bounded at the bottom by organic-rich stylolite surfaces. Authigenic and euhedral dolomite and calcite crystals are associated with the anhydrite. Traces of pyrite, galena and chalcopyrite are present along the stylolite surfaces suggesting supply of fresh water from the underlying sandstone at highly reducing conditions of burial. The δ<sup>34</sup>S of sulphate in the Basal Anhydrite averages 15 ‰ (CDT) and falls within the isotopic composition of the anhydrite in the Cretaceous Maha Sarakham Formation proper and the Cretaceous values of marine evaporites. Measured δ<sup>18</sup>O in dolomite range from ?4·37 to ?14·26‰ (PDB) suggesting a re-equilibration of dolomite with basinal water depleted in <sup>18</sup>O and possible recrystallization of dolomite under relatively elevated temperatures. The δ<sup>13</sup>C, however, varies from +1·57 to ?2·53‰ (PDB) suggesting a contribution of carbon from oxidation of organic matter. This basal anhydrite bed, similar to basinwide beds found at the bottom of many giant evaporite sequences, has always been considered to be depositional. Here, at the base of the Maha Sarakham Formation, we demonstrate that the anhydrite is diagenetic in origin and was formed by accumulation of original anhydrite by dissolution of interbedded halite from waters circulating though the underlying aquifer: it represents an `upside-down' caprock.     

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.     

Rise in seawater sulphate concentration associated with the Paleoproterozoic positive carbon isotope excursion: evidence from sulphate evaporites in the ∼2.2–2.1 Gyr shallow‐marine Lucknow Formation,South Africa

Abstract Past oceanic sulphate concentration is important for understanding how the oceans’ redox state responded to atmospheric oxygen levels. The absence of extensive marine sulphate evaporites before ～1.2 Gyr probably reflects low seawater sulphate and/or higher carbonate concentrations. Sulphate evaporites formed locally during the 2.22–2.06 Gyr Lomagundi positive δ¹³C excursion. However, the ～2.2–2.1 Gyr Lucknow Formation, South Africa, provides the first direct evidence for seawater sulphate precipitation on a carbonate platform with open ocean access and limited terrestrial input. These marginal marine deposits contain evidence for evaporite molds, pseudomorphs after selenite gypsum, and solid inclusions of Ca‐sulphate in quartz. Carbon and sulphur isotope data match the global record and indicate a marine source of the evaporitic brines. The apparent precipitation of gypsum before halite requires ≥2.5 mm L^?1 sulphate concentration, higher than current estimates for the Paleoproterozoic. During the Lomagundi event, which postdates the 2.32 Gyr initial rise in atmospheric oxygen, seawater sulphate concentration rose from Archean values of ≤200 μm L^?1, but dropped subsequently because of higher pyrite burial rates and a lower oceanic redox state.     

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.     

Effect of pedogenesis on the stable isotopic composition of calcretes and n‐alkanes: Implications for palaeoenvironmental reconstruction

In a fluvial system, depending on sub‐aerial exposure, non‐pedogenic pond calcretes can be modified into pedogenic calcretes. The present study attempts to understand the effect of sub‐aerial exposure and pedogenesis on calcretes using carbon and oxygen isotopic composition. For this purpose, two profiles (profile‐A and profile‐B) from the same stratigraphic level in Rayka from the western part of India were selected. The profiles are separated by a distance of 500 m and showed differences in calcrete characteristics. In profile‐A, the calcretes showed pedogenic features (root traces and void filling spar) whereas calcretes in profile‐B showed non‐pedogenic characteristics (fine laminations). However, some of the calcretes in profile‐A exhibited remnants of fine laminations suggesting that initially the calcretes had a non‐pedogenic origin but were modified due to pedogenesis. In profile‐A, the carbon and oxygen isotope values of pedogenic calcrete (δ¹³C_PC and δ¹⁸O_PC) showed more variation compared with non‐pedogenic pond calcretes (δ¹³C_SPC and δ¹⁸O_SPC) in profile‐B. The δ¹³C_PC and δ¹³C_SPC values exhibited a spread of 3·0‰ and 1·3‰, respectively, and δ¹⁸O_PC and δ¹⁸O_SPC values showed a spread of 2·3‰ and 1·3‰, respectively. The differences in the isotopic composition between the two profiles suggest that pedogenesis controlled the isotopic inheritance in calcretes. In addition, the carbon isotopic composition of organic matter (δ¹³C_OM) and n‐alkanes (δ¹³C_n‐alk) that forms the basis of palaeovegetational reconstruction have also been measured to understand the effect of pedogenesis on organic matter in both of the profiles. The average δ¹³C_OM values in profile‐A and profile‐B are ?23·4‰ and ?21·1‰, respectively. The disparity in δ¹³C_OM values is a result of the difference in the sources and preservation of organic matter. However, the δ¹³C_n‐alk values show a similar trend in profile‐A and profile‐B, indicating that sources of n‐alkanes are the same in both of the profiles and δ¹³C_n‐alk values are unaffected by the pedogenic modifications.     

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.     

Neogene evaporites in desert volcanic environments: Atacama Desert, northern Chile

The Upper Miocene and Pliocene evaporite deposits of the Atacama Desert of northern Chile (Hilaricos and Soledad Formations) are among the few non‐marine evaporites in which aridity not only formed the deposits, but has also preserved them almost unaltered under near‐surface conditions. These deposits are largely composed of displacive Ca sulphate and halite together with minor amounts of glauberite, thenardite and polyhalite. However, at the base and top of these deposits, there are also beds of gypsum crystal pseudomorphs that originally formed as free‐growth forms within shallow brine bodies, rather than as displacive sediments. The halite is present as interstitial cement, displacive cubes and shallow‐water, bottom‐growth chevron crusts. Most of the calcium sulphate is presently anhydrite, pseudomorphous after gypsum, that was the primary depositional sulphate mineral. The secondary anhydrite formed under early diagenetic conditions after slight burial (some metres) resulting from the effect of strongly evolved pore brines. The anhydrite has been preserved without rehydration during late diagenetic and exhumation stages on account of the arid environment of the Atacama Desert. Both the Hilaricos and the Soledad Formations contain geochemical markers indicating that these Neogene evaporites had a largely non‐marine origin. Bromine content in the halite is very low (few p.p.m.), indicating neither a sedimentological relation with sea water nor the likelihood of direct recycling of prior marine halites. Moreover, the δ³⁴S of sulphates (+4·5‰ to +9‰) also reflects a non‐marine origin, with a strong volcanic influence, although some recycling of Mesozoic marine sulphates cannot be ruled out. δ³⁴S of dissolved sulphate from hot springs and streams in the area commonly displays positive values (+2‰ to +10‰). Leaching of oxidized sulphur and chlorine compounds from volcanoes and epithermal ore bodies, very common in the associated drainage areas, have been the main contribution to the accumulation of evaporites. The sedimentary and diagenetic evolution of the Hilaricos and Soledad evaporites (based on lithofacies analysis) provides information about the palaeohydrological conditions in the Central Depression of northern Chile during the Neogene. In addition, the diagenesis and exhumation history of these evaporites confirms the persistence of strongly arid conditions from Late Miocene until the present. A final phase of tectonism took place permitting the internal drainage to change and open to the sea, resulting in dissolution and removal of a significant portion of these deposits. Despite the extensive dissolution, the remaining evaporites have undergone little late exhumational hydration.     

An Upper Aptian saline pan/lake system from the Brazilian equatorial margin: integration of facies and isotopes

Facies and isotope (Sr and S) data were combined in order to discuss the genesis and palaeohydrology of an Upper Aptian evaporite succession formed during the initial development of an intra-continental rift from northern Brazil. Comparison of facies distribution between two investigated areas shows: (i) stable, well-stratified and hypersaline lakes with periods of anoxia and closure in the eastern margin of the basin, where there was evaporite precipitation only in central lake environments; and (ii) more ephemeral conditions in the eastern margin of the basin, where a saline pan complex developed and evaporite precipitation took place mainly in marginal salinas and surrounding mudflats. In both areas, expansion/contraction cycles developed as sedimentation took place, accompanied by a decrease and then an increase in ⁸⁷Sr/⁸⁶Sr- and δ³⁴S-isotope values. This, combined with the wide distribution of Sr- and S-isotope data within individual depositional cycles, as well as petrographic and scanning electronic microscopic (SEM) images, led to the conclusion that diagenesis was not enough to obscure the primary geochemical signature. A non-marine brine source is suggested by ⁸⁷Sr/⁸⁶Sr ratios between 0·707824 and 0·709280, which are higher than those from Upper Aptian sea water (i.e. between 0·70720 and 0·70735). The δ³⁴S value varies from 16·12 to 17·89‰ in the eastern margin of the basin, which is in disagreement with Upper Aptian marine values (13 to 16‰). Both geochemical tracers were influenced by facies characteristics, and thus a model is provided, where ⁸⁷Sr/⁸⁶Sr values respond to changes in expansion and contraction episodes of saline pan/lake systems.     

Syn-sedimentary hydrothermal dolomites in a lacustrine rift basin: Petrographic and geochemical evidence from the lower Cretaceous Erlian Basin,Northern China

Dolomites occur extensively in the lower Cretaceous along syn-sedimentary fault zones of the Baiyinchagan Sag, westernmost Erlian Basin, within a predominantly fluvial–lacustrine sedimentary sequence. Four types of dolomite are identified, associated with hydrothermal minerals such as natrolite, analcime and Fe-bearing magnesite. The finely-crystalline dolomites consist of anhedral to subhedral crystals (2 to 10 μm), evenly commixed with terrigenous sediments that occur either as matrix-supporting grains (Fd1) or as massive argillaceous dolostone (Fd2). Medium-crystalline (Md) dolomites are composed of subhedral to euhedral crystals aggregates (50 to 250 μm) and occur in syn-sedimentary deformation laminae/bands. Coarse-crystalline (Cd) dolomites consist of non-planar crystals (mean size >1 mm), and occur as fracture infills cross-cutting the other dolomite types. The Fd1, Md and Cd dolomites have similar values of δ¹⁸O (−20·5 to −11·0‰ Vienna PeeDee Belemnite) and δ¹³C (+1·4 to +4·5‰ Vienna PeeDee Belemnite), but Fd2 dolomites are isotopically distinct (δ¹⁸O −8·5 to −2·3‰ Vienna PeeDee Belemnite; δ¹³C +1·4 to +8·6‰ Vienna PeeDee Belemnite). Samples define three groups which differ in light rare-earth elements versus high rare-earth elements enrichment/depletion and significance of Tb, Yb and Dy anomalies. Medium-crystalline dolomites have signatures that indicate formation from brines at very high temperature, with salinities of 11·8 to 23·2 eq. wt. % NaCl and T_h values of 167 to 283°C. The calculated temperatures of Fd1 and Cd dolomites extend to slightly lower values (141 to 282°C), while Fd2 dolomites are distinctly cooler (81 to 124°C). These results suggest that the dolomites formed from hydrothermal fluid during and/or penecontemporaneous with sediment deposition. Faults and fractures bounding the basin were important conduits through which high-temperature Mg-rich fluids discharged, driven by an abnormally high heat flux associated with local volcanism. It is thought that differing amounts of cooling and degassing of these hydrothermal fluids, and of mixing with lake waters, facilitated the precipitation of dolomite and associated minerals, and resulted in the petrographic and geochemical differences between the dolomites.     

Meteoric diagenesis and dedolomite fabrics in precursor primary dolomicrite in a mixed carbonate–evaporite system

Dedolomitization is a common diagenetic process in shallow burial environments and is often associated with sulphates in mixed carbonate‐evaporite successions. In these settings, elevated Ca²⁺/Mg²⁺ ratios necessary for dedolomitization result from the dissolution of sulphate phases by the incursion of undersaturated groundwater. Reported dedolomite textures from other studies are varied, but the most prevalent is a rhombic texture interpreted to result from the partial to complete pseudomorphic replacement of secondary dolomite rhombs formed in the burial diagenetic realm. In this study of primary cryptocrystalline to finely crystalline dolomicrites in the Prairie Evaporite Formation of north‐eastern Alberta, dedolomitization has resulted in sutured to loosely packed mosaics of dedolomite that range from subhedral to distinctly euhedral (rhombic) crystal fabrics; however, no prior aggrading neomorphism producing dolomite rhombs is evident in the precursor dolomicrites. Non‐pseudomorphic dedolomitization of the dolomicrites results in textures that include rhombic dedolomite crystals with cloudy cores comprising remnant dolomicrite and clear rims. These textures are similar to those observed in the pseudomorphic dedolomitization of secondary dolomite rhombs. The Prairie Evaporite Formation of north‐eastern Alberta has experienced extensive karstification near the erosional margin of the sedimentary succession. Dedolomitization of dolomicrites occurs in marker beds within the Prairie Evaporite succession associated with evaporite karstification. Along with stratigraphic and petrographic considerations, stable isotope results support the interpretation of a shallow dedolomitization event influenced by meteoric waters derived from the basin margin. Negative δ ¹⁸O and low δ ¹³C values (averages of −13·6‰_VPDB and 0·5‰_VPDB, respectively) of the dedolomite, compared with those of the primary dolomicrite (averages of −6·0‰_VPDB and 1·2‰_VPDB, respectively), point to isotopically light diagenetic fluids. These results show that rhombic dedolomite textures can form through shallow, non‐pseudomorphic dedolomitization of dolomicrites by meteoric fluids in the presence of sulphates, with resulting textures that are similar to the pseudomorphic dedolomitization of secondary dolomite rhombs.     

Columnar calcites as testimony of diagenetic overprinting at the boundary between Upper Tournaisian dolomites and limestones (Belgium): multiple origins for apparently similar features

In topographic flat areas, sedimentary settings may vary from one outcrop to another. In these settings, calcite precipitates may yield macroscopically similar columnar features, although they are products of different sedimentary or diagenetic processes. Three columnar calcite crystal fabrics, i.e. rosettes, palisade crusts and macro-columnar crystal fans, have been differentiated near and at the contact between Upper Tournaisian dolomites and limestones along the southern margin of the Brabant-Wales Palaeohigh. Their petrographic characteristics, and geochemical and fluid inclusion data provide information on the (dia)genetic processes involved. Rosettes composed of non-luminescent columnar calcite crystal fans (1–5 cm in diameter) developed on top of one another, forming discrete horizons in repetitive sedimentary cycles. The cycles consist of three horizons: (I) a basal horizon with fragments from the underlying horizon, (II) a micrite/microspar horizon with incipient glaebules, (III) an upper horizon consisting of calcite rosettes, with desiccation features. The petrographical features and δ¹⁸O signatures of −10·0 to −5·5‰ and δ¹³C values of −5·5 to −3·2‰ support either evaporative growth, an evaporative pedogenic origin, or overprinting of marine precipitates. Palisade crusts, composed of a few to 10 mm long non-luminescent calcite crystals, coat palaeokarst cavities. Successive palisade growth-stages occur which are separated by thin laminae of micrite or detrital quartz, displaying a geopetal arrangement. Palisade crusts are interpreted as intra-Mississippian speleothems. This interpretation is supported by their petrographic characteristics and isotopic signature (δ¹⁸O = −8·7 to −6·5‰ and δ¹³C = −4·8 to −2·5‰). Macro-columnar crystals, 1–50 cm long, developed mainly perpendicular to cavity walls and dolomite clasts. Crystal growth stages in the macro-columnar crystals are missing. δ¹⁸O values vary between −16·4 and −6·8‰ and δ¹³C values between −5·2 and −0·9‰. These features possibly support a late diagenetic high temperature precipitation in relation to hydrothermal karstification.     

Deciphering the depositional environment of the laminated Crato fossil beds (Early Cretaceous,Araripe Basin,North‐eastern Brazil)

The laminated limestones of the Early Cretaceous Crato Formation of the Araripe Basin (North‐eastern Brazil) are world‐famous for their exceptionally well‐preserved and taxonomically diverse fossil fauna and flora. Whereas the fossil biota has received considerable attention, only a few studies have focused on the sedimentary characteristics and palaeoenvironmental conditions which prevailed during formation of the Crato Fossil Lagerstätte. The Nova Olinda Member represents the lowermost and thickest unit (up to 10 m) of the Crato Formation and is characterized by a pronounced rhythmically bedded, pale to dark lamination. To obtain information on palaeoenvironmental conditions, sample slabs derived from three local stratigraphic sections within the Araripe Basin were studied using high‐resolution multiproxy techniques including detailed logging, petrography, μ‐XRF scanning and stable isotope geochemistry. Integration of lithological and petrographic evidence indicates that the bulk of the Nova Olinda limestone formed via authigenic precipitation of calcite from within the upper water column, most probably induced and/or mediated by phytoplankton and picoplankton activity. A significant contribution from a benthonic, carbonate‐secreting microbial mat community is not supported by these results. Deposition took place under anoxic and, at least during certain episodes, hypersaline bottom water conditions, as evidenced by the virtually undisturbed lamination pattern, the absence of a benthonic fauna and by the occurrence of halite pseudomorphs. Input of allochthonous, catchment‐derived siliciclastics to the basin during times of laminite formation was strongly reduced. The δ¹⁸O values of authigenic carbonate precipitates (between ?7·1 and ?5·1‰) point to a ¹⁸O‐poor meteoric water source and support a continental freshwater setting for the Nova Olinda Member. The δ¹³C values, which are comparatively rich in ¹³C (between ?0·1 and +1·9‰), are interpreted to reflect reduced throughflow of water in a restricted basin, promoting equilibration with atmospheric CO₂, probably in concert with stagnant conditions and low input of soil‐derived carbon. Integration of lithological and isotopic evidence indicates a shift from closed to semi‐closed conditions towards a more open lake system during the onset of laminite deposition in the Crato Formation.     

Stable isotopic and elemental characteristics of recent tufa from a karstic Krka River (south‐east Slovenia): useful environmental proxies?

Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO₂ degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ¹³C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO₂ degassing and tufa precipitation rate downstream. The Δ¹³C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous ¹²CO₂ degassing downstream leaving the carbon pool enriched in ¹³C. In the case of oxygen, the isotope fractionation (Δ¹⁸O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ¹⁸O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ¹⁸O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.     

A Fluid Inclusion Study of Vein-type Copper Mineralization in the East Wulasigou Pb–Zn–Cu Deposit, Altay, Northwestern China

The Wulasigou Cu-Pb-Zn deposit,located 15 km northwest of Altay city in Xinjiang,is one of many Cu-Pb-Zn polymetallic deposits in the Devonian Kelan volcanic-sedimentary basin in southern Altaids.Two mineralizing periods can be distinguished:the marine volcanic sedimentary PbZn mineralization period,and the metamorphic hydrothermal Cu mineralization period,which is further divided into an early bedded foliated quartz vein stage(Q1) and a late sulfide-quartz vein stage(Q2) crosscutting the foliation.Four types of fluid inclusions were recognized in the Q1 and Q2 quartz from the east orebodies of the Wulasigou deposit:H_2O-CO_2 inclusions,carbonic fluid inclusions,aqueous fluid inclusions,and daughter mineral-bearing fluid inclusions.Microthermometric studies show that solid CO_2 melting temperatures(T_(m,CO2)) of H_2O-CO_2 inclusions in Ql are from-62.3℃ to-58.5C,clathrate melting temperatures(T_(m,clath)l) are from 0.5 C to 7.5 C,partial homogenization temperatures(T_(h,CO2)) vary from 3.3℃ to 25.9℃(to liquid),and the total homogenization temperatures(T_(h,tot)) vary from 285℃ to 378℃,with the salinities being 4.9%-15.1%NaCl eqv.and the CO_2-phase densities being 0.50-0.86 g/cm~3.H_2O-CO_2 inclusions in Q2 have T_(m,CO_2) from-61.9℃ to-56.9℃,T_(m,clath)from 1.3℃ to 9.5℃,T_(h,CO2) from 3.4℃ to 28.7℃(to liquid),and T_(h,tot) from 242℃ to 388℃,with the salinities being 1.0%-15.5%NaCl eqv.and the CO_2-phase densities being 0.48-0.89 g/cm~3.The minimum trapping pressures of fluid inclusions in Q1 and Q2 are estimated to be 260-360 MPa and180-370 MPa,respectively.The δ~(34)S values of pyrite from the volcanic sedimentary period vary from2.3‰ to 2.8‰(CDT),and those from the sulfide-quartz veins fall in a narrow range of-1.9‰ to 2.6‰(CDT).The δD values of fluid inclusions in Q2 range from-121.0‰ to-100.8‰(SMOW),and theδ~(18)O_(H2O) values calculated from δ~(18)O of quartz range from-0.2‰ to 8.3‰(SMOW).The δD-δ~(18)O_(H2O)data are close to the magmatic and metamorphic fields.The fluid inclusion and stable isotope data documented in this study indicate that the vein-type copper mineralization in the Wulasigou Pb-Zn-Cu deposit took place in an orogenic-metamorphic enviroment.     

Origin of facies zonation in microbial carbonate platform slopes: Clues from trace element and stable isotope geochemistry (Middle Triassic,Dolomites, Italy)

Limestones containing radiaxial fibrous cements were sampled along the southern slope of the late Anisian (Middle Triassic) Latemar carbonate platform in the Dolomites, northern Italy. The Latemar upper slopes comprise massive microbial boundstone, whereas lower slopes are made of clinostratified grainstone, rudstone and breccia. Samples are representative of a seawater column from near sea‐level to an aphotic zone at about 500 m water depth. Radiaxial fibrous cements were analyzed for carbon (δ¹³C) and oxygen (δ¹⁸O) stable isotopic composition, as well as major and trace element content, to shed light on the origin of the slope facies zonation. The δ¹³C vary between 1·7‰ and 2·3‰ (Vienna Pee‐Dee Belemnite), with lowest values at palaeo‐water depths between 70 m and 300 m. Radiaxial fibrous cements yielded seawater‐like rare earth element patterns with light rare earth element depletion (Nd_SN/Yb_SN ≈ 0·4), superchondritic yttrium/holmium ratios (≈55) and negative cerium anomalies. Cadmium reaches maximum values of ca 0·5 to 0·7 μg/g at palaeo‐water depths between 70 m and 300 m; barium contents (0·8 to 1·8 μg/g) increase linearly with depth. The downslope patterns of δ¹³C and cadmium suggest increased nutrient and organic matter contents at depths between ca 70 m and 300 m and point to an active biological pump. The peak in cadmium and the minimum of δ¹³C mark a zone of maximum organic matter respiration and high nutrient and organic matter availability. The base of this zone at ca 300 m depth corresponds with the transition from massive microbial boundstone to clinostratified grainstone, rudstone and breccia. The microbial boundstone facies apparently formed only in seawater enriched in organic matter, possibly because this organic matter sustained benthic microbial communities at Latemar. The base of slope microbialites on high‐relief microbial carbonate platforms may be a proxy for the depth to maximum respiration zones of Palaeozoic and Mesozoic periplatform basins.     

Porewater sulphur geochemistry and fossil preservation during phosphate diagenesis in a Lower Cretaceous shelf mudstone

Lower Cretaceous mudstones exposed at Speeton in North Yorkshire, UK, contain lobsters and burrows preserved in diagenetic phosphate concretions. Isotopic compositions of sulphur in both diagenetic sulphide and structural sulphate in diagenetic phosphate have been measured in an attempt to constrain diagenetic porewater chemistry. The occurrence of phosphatized and pyritized lobsters and similarly preserved burrows, allows a detailed comparison of these microenvironments with the host sediments. Host sediments are extensively bioturbated and characterized by very light sulphide isotopic compositions (mean sulphide δ³⁴S = –48·3 ± 3‰ (1σ, n = 19)) and sulphate isotopic compositions that are lighter than Lower Cretaceous seawater sulphate (mean sulphate δ³⁴S = +8·7 ± 3·2‰ (1σ, n = 19)). These isotopic values can be explained by the action of bioturbating macrofauna; the introduction of oxygen in ventilating seawater results in the oxidation of early formed isotopically light pyrite, resulting in porewater sulphate that is enriched in ³²S. Subsequent pyrite formation via bacteriogenic reduction of isotopically light porewater sulphate leads to the formation of isotopically light pyrite, whilst residual porewater sulphate apparently remains relatively enriched in the ³²S isotope. Sulphur isotopic values for the burrows are very different; sulphide isotopic compositions average –34·4 ± 0·4‰ (1σ, n = 3) and sulphate isotopic compositions average –14·4 ± 6·6‰ (1σ, n = 4). These isotopic compositions are the result of rapid development of closed system conditions in burrows, resulting in the build-up of acidity necessary for phosphate precipitation and coprecipitation of isotopically light sulphate (formed by oxidation of isotopically light sulphide surrounding the burrows). Lobster shell isotopic compositions fall between these two groups. On the basis of their isotopic compositions, some lobsters appear to have died close to the sediment–water interface, whilst others appear to have been buried (in burrows) prior to death.     

Palaeoproterozoic magnesite: lithological and isotopic evidence for playa/sabkha environments

Magnesite forms a series of 1‐ to 15‐m‐thick beds within the ≈2·0 Ga (Palaeoproterozoic) Tulomozerskaya Formation, NW Fennoscandian Shield, Russia. Drillcore material together with natural exposures reveal that the 680‐m‐thick formation is composed of a stromatolite–dolomite–‘red bed’ sequence formed in a complex combination of shallow‐marine and non‐marine, evaporitic environments. Dolomite‐collapse breccia, stromatolitic and micritic dolostones and sparry allochemical dolostones are the principal rocks hosting the magnesite beds. All dolomite lithologies are marked by δ¹³C values from +7·1‰ to +11·6‰ (V‐PDB) and δ¹⁸O ranging from 17·4‰ to 26·3‰ (V‐SMOW). Magnesite occurs in different forms: finely laminated micritic; stromatolitic magnesite; and structureless micritic, crystalline and coarsely crystalline magnesite. All varieties exhibit anomalously high δ¹³C values ranging from +9·0‰ to +11·6‰ and δ¹⁸O values of 20·0–25·7‰. Laminated and structureless micritic magnesite forms as a secondary phase replacing dolomite during early diagenesis, and replaced dolomite before the major phase of burial. Crystalline and coarsely crystalline magnesite replacing micritic magnesite formed late in the diagenetic/metamorphic history. Magnesite apparently precipitated from sea water‐derived brine, diluted by meteoric fluids. Magnesitization was accomplished under evaporitic conditions (sabkha to playa lake environment) proposed to be similar to the Coorong or Lake Walyungup coastal playa magnesite. Magnesite and host dolostones formed in evaporative and partly restricted environments; consequently, extremely high δ¹³C values reflect a combined contribution from both global and local carbon reservoirs. A ¹³C‐rich global carbon reservoir (δ¹³C at around +5‰) is related to the perturbation of the carbon cycle at 2·0 Ga, whereas the local enhancement in ¹³C (up to +12‰) is associated with evaporative and restricted environments with high bioproductivity.