Formation of modern dolomite in hypersaline pans of the Western Cape,South Africa

Authigenic calcite and dolomite and biogenic aragonite occur in Holocene pan sediments in a Mediterranean‐type climate on the western coastal plain of South Africa. Sediment was analysed from a Late Pleistocene coastal pan at Yzerfontein and four Holocene inland pans ranging from brackish to hypersaline. The pans are between 0·08 and 0·14 km² in size. The δ¹⁸O_PDB values of carbonate minerals in the pan sediments range from ?2·41 to 5·56‰ and indicate precipitation from evaporative waters. Covariance of total organic content and percentage carbonate minerals, and the δ¹³C_PDB values of pan carbonate minerals (?8·85 to ?1·54‰) suggest that organic matter degradation is a significant source of carbonate ions. The precipitation of the carbonate minerals, especially dolomite, appears to be mediated by sulphate‐reducing bacteria in the black sulphidic mud zone found in the brine‐type hypersaline pans. The knobbly, sub‐spherical texture of the carbonate minerals suggests that the precipitation of the carbonate minerals, particularly dolomite, is related to microbial processes. The ⁸⁷Sr/⁸⁶Sr ratios of pan carbonate minerals (0·7108 to 0·7116) are slightly higher than modern sea water and indicate a predominantly sea water (marine aerosol) source for calcium (Ca²⁺) ions with relatively minor amounts of Ca²⁺ derived from the chemical weathering of bedrock.     

Physical and chemical growth conditions of Ordovician organogenic deep-water dolomite concretions: implications for the δ18O of Early Palaeozoic sea water

The estimated depth of formation of authigenic dolomite concretions in the Middle Ordovician Cloridorme Formation, Quebec, ranges from < 1 m to 150–200 m below sea floor (mbsf) (mostly between < 1 and 25 mbsf), based on centre‐to‐margin variations in minus‐cement porosity (80–90% to 45–75%). Formation depths are > 350 mbsf (25–17% porosity) in the Lower Ordovician Levis Formation. Outward‐decreasing δ¹³C_VPDB values (10·2–0·8‰) suggest precipitation in the methane generation zone with an increasing contribution of light carbonate derived by advection from thermocatalytic reactions at depth. Anomalously low δ¹⁸O_VPDB values (centre‐to‐margin variations of ?0·4 to ?7·5‰) give reasonable temperatures for the concretion centres only if the δ¹⁸O of Ordovician sea water was negative (?6‰) and the bottom water was warm (> 15 °C). The 3–5‰ lower values for the concretion margins compared with the centres can be explained if, in addition, volcanic‐ash alteration, organic‐matter decomposition and/or advection of ¹⁸O‐depleted water lowered the δ¹⁸O of the pore water further by 2·0–4·0‰ during the first 25–200 m of burial. Reasonable growth temperatures for the margins of 17–20 °C are compatible with a lowering of the isotopic ratios by 1 to < 1·3‰ as a temperature effect. The systematic concentric isotope zonation of the concretions suggests that the well‐ordered near‐stoichiometric dolomite is a primary feature and not the result of recrystallization. Diagenetic dolomite beds of the Cloridorme Formation appear to have formed by coalescence of concretions, as shown by randomly sampled traverses that indicate formation at different subsurface depths. Growth of the Cloridorme dolomites was probably limited by calcium availability, at least 50% of which was derived from connate water, and the remainder by diffusion from sea water. Dolomite precipitation was favoured over calcite by very high sedimentation rates, the abundance of marine organic matter in the host sediment and a correspondingly thin sulphate reduction zone. Deep‐seated concretion growth in the Levis Formation required either internal sources for the participating ions (carbonate dissolution event) or porewater advection along faults.     

Disseminated ‘jigsaw piece’ dolomite in Upper Jurassic shelf sandstones,Central North Sea: an example of cement growth during bioturbation?

Unusual textural and chemical characteristics of disseminated dolomite in Upper Jurassic shelf sediments of the North Sea have provided the basis for a proposed new interpretation of early diagenetic dolomite authigenesis in highly bioturbated marine sandstones. The dolomite is present throughout the Franklin Sandstone Formation of the Franklin and Elgin Fields as discrete, non‐ferroan, generally unzoned, subhedral to highly anhedral ‘jigsaw piece’ crystals. These are of a similar size to the detrital silicate grains and typically account for ≈5% of the rock volume. The dolomite crystals are never seen to form polycrystalline aggregates or concretions, or ever to envelop the adjacent silicate grains. They are uniformly dispersed throughout the sandstones, irrespective of detrital grain size or clay content. Dolomite authigenesis predated all the other significant diagenetic events visible in thin section. The dolomite is overgrown by late diagenetic ankerite, and bulk samples display stable isotope compositions that lie on a mixing trend between these components. Extrapolation of this trend suggests that the dolomite has near‐marine δ¹⁸O values and low, positive δ¹³C values. The unusual textural and chemical characteristics of this dolomite can all be reconciled if it formed in the near‐surface zone of active bioturbation. Sea water provided a plentiful reservoir of Mg and a pore fluid of regionally consistent δ¹⁸O. Labile bioclastic debris (e.g. aragonite, Mg‐calcite) supplied isotopically positive carbon to the pore fluids during shallow‐burial dissolution. Such dissolution took place in response to the ambient ‘calcite sea’ conditions, but may have been catalysed by organic matter oxidation reactions. Bioturbation not only ensured that the dissolving carbonate was dispersed throughout the sandstones, but also prohibited coalescence of the dolomite crystals and consequent cementation of the grain framework. Continued exchange of Mg²⁺ and Ca²⁺ with the sea‐water reservoir maintained a sufficient Mg/Ca ratio for dolomite (rather than calcite) to form. Irregular crystal shapes resulted from dissolution, of both the dolomite and the enclosed fine calcitic shell debris, before ankerite precipitation during deep‐burial diagenesis.     

Holocene meteoric dolomitization of Pleistocene limestones, North Jamaica

Wholesale removal of the unstable carbonate phases aragonite and Mg-calcite, and precipitation of calcite and dolomite is currently taking place where phreatic waters (the modern water table) invade 120,000-year-old Pleistocene biolithites (Falmouth Formation), North Jamaica. Pleistocene rocks presently in the vadose zone are relatively unaltered, and consist of mineralogically unstable scleractinian biolithites. At the water table, a narrow zone of solution, a ‘water table cave’ is commonly encountered. Below the water table the rocks are invariably more highly altered than those above. Mg-calcites are very rare, and considerable dissolution of aragonite has commonly occurred. Dolomite occurs as 8–25 μm, subhedral to euhedral crystals replacing micrite, or precipitated as void linings. The isotopic composition of the dolomite (δO¹⁸=-1·0 %0, δC¹³=-8·4 %0), and its high strontium content (3000 p.p.m.) suggest precipitation as CO₂-oversaturated meteoric groundwaters invade the mineralogically unstable biolithites, dissolve Mg-calcites and Sr-rich aragonites, and de-gas. Because some dolomitized rocks are enriched in magnesium relative to unaltered biolithites, addition of magnesium to the system is necessitated, and is probably derived from sea water in the mixing zone. Phreatic meteoric diagenesis is thus demonstrated to be a rapid process, and to be capable of dolomitization.     

Marine cements in mid-Tertiary cool-water shelf limestones of New Zealand and southern Australia

Large areas of southern Australia and New Zealand are covered by mid‐Tertiary limestones formed in cool‐water, shelf environments. The generally destructive character of sea‐floor diagenesis in such settings precludes ubiquitous inorganic precipitation of carbonates, yet these limestones include occasional units with marine cements: (1) within rare in situ biomounds; (2) within some stacked, cross‐bedded sand bodies; (3) at the top of metre‐scale, subtidal, carbonate cycles; and (4) most commonly, associated with certain unconformities. The marine cements are dominated by isopachous rinds of fibrous to bladed spar, interstitial homogeneous micrite and interstitial micropeloidal micrite, often precipitated sequentially in that order. Internal sedimentation of microbioclastic micrite may occur at any stage. The paradox of marine‐cemented limestone units in an overall destructive cool‐water diagenetic regime may be explained by the precipitation of cement as intermediate Mg‐calcite from marine waters undersaturated with respect to aragonite. In some of the marine‐cemented limestones, aragonite biomoulds may include marine cement/sediment internally, suggesting that dissolution of aragonite can at times be wholly marine and not always involve meteoric influences. We suggest that marine cementation occurred preferentially, but not exclusively, during periods of relatively lowered sea level, probably glacio‐eustatically driven in the mid‐Tertiary. At times of reduced sea level, there was a relative increase in both the temperature and the carbonate saturation state of the shelf waters, and the locus of carbonate sedimentation shifted towards formerly deeper shelf sites, which now experienced increased swell wave and/or tidal energy levels, fostering sediment abrasion and reworking, reduced sedimentation rates and freer exchange of sediment pore‐waters. Energy levels were probably also enhanced by increased upwelling of cold, deep waters onto the Southern Ocean margins of the Australasian carbonate platforms, where water‐mass mixing, warming and loss of CO₂ locally maintained critical levels of carbonate saturation for sea‐floor cement precipitation and promoted the phosphate‐glauconite mineralization associated with some of the marine‐cemented limestone units.     

Oil seepage and carbonate formation: A case study from the southern Gulf of Mexico

Oil seeps from the southern Gulf of Mexico can be regarded as natural laboratories where the effect of crude oil seepage on chemosynthesis‐based communities and carbonate precipitation can be studied. During R/V Meteor cruise 114 the seep sites UNAM (Universidad Nacional Autónoma de México) Ridge, Mictlan Knoll and Tsanyao Yang Knoll (Bay of Campeche, southern Gulf of Mexico) were investigated and sampled for authigenic carbonate deposits containing large amounts of liquid oil and solid asphalt. The δ¹³C values of individual carbonate phases including: (i) microcrystalline matrix aragonite and calcite; (ii) grey, cryptocrystalline to microcrystalline aragonite; and (iii) clear, fibrous aragonite cement, are between ?30‰ and ?20‰, agreeing with oil as the primary carbon source. Raman spectra reveal that residual heavy oils from all sites are immature and most likely originate from the same reservoir. Geochemical batch modelling using the software code PHREEQC demonstrates how sulphate‐driven oxidation of oil‐derived low‐molecular to high‐molecular weight hydrocarbons affects carbonate saturation state, and shows that the oxidation state of carbon in hydrocarbon compounds and oxidation rates of hydrocarbons control carbonate saturation and precipitation at oil seeps. Phase‐specific trace and rare earth element contents of microcrystalline aragonite and calcite, grey cryptocrystalline aragonite and clear aragonite were determined, revealing enrichment in light rare earth elements for grey aragonite. By comparing trace element patterns of carbonates with those of associated oils, it becomes apparent that liquid hydrocarbons constitute an additional source of trace metals to sedimentary pore waters. This work not only demonstrates that the microbial degradation of oil at seeps may result in the precipitation of carbonate minerals, it also elucidates that trace metal inventories of seep carbonates archive diagnostic elemental patterns, which can be assigned to the presence of heavy hydrocarbons in interstitial pore waters.     

Precipitation of dolomite using sulphate-reducing bacteria from the Coorong Region, South Australia: significance and implications

Dolomite was successfully precipitated in culture experiments that simulated microbiogeochemical conditions prevailing during late stages of evaporation in ephemeral, hypersaline dolomitic lakes of the Coorong region, South Australia. Analyses of lake- and pore-water samples document rapid geochemical changes with time and depth in both dolomitic and non-dolomitic lakes. Extremely high sulphate and magnesium ion concentrations in lake waters decline rapidly with depth in pore waters throughout the sulphate-reduction zone, whereas carbonate concentrations in pore waters reach levels up to 100 times those of normal sea water. Ultimately, sulphate is totally consumed and no solid sulphate is recorded in the dolomitic lake sediments. ‘Most probable number’ calculations of lake sediment samples record the presence of large populations of sulphate-reducing bacteria, whereas sulphur-isotope analyses of lake-water samples indicate microbial fractionation in all the lakes studied. Viable populations of microbes from the lake sediments were cultured in anoxic conditions in the laboratory. Samples were then injected into vials containing sterilized clastic or carbonate grains, or glass beads, immersed in a solution that simulated the lake water. Falls in the levels of sulphate and rising pH in positive vials were interpreted as indicating active bacterial sulphate reduction accompanied by increased concentrations of carbonate. Within 2 months, sub-spherical, sub-micron-size crystals of dolomite identical to those of lake sediments were precipitated. It is concluded that bacterial sulphate reduction overcomes kinetic constraints on dolomite formation by removing sulphate and releasing magnesium and calcium ions from neutral ion pairs, and by generating elevated carbonate concentrations, in a hypersaline, strongly electrolytic solution. The results demonstrate that bacterial sulphate reduction controls dolomite precipitation in both the laboratory experiments and lake sediments. It is proposed that dolomite formation, through bacterial sulphate reduction, provides a process analogue applicable to thick platformal dolostones of the past, where benthic microbial communities were the sole or dominant colonizers of shallow marine environments.     

'Pseudobreccias' revealed as calcrete mottling and bioturbation in the Late Dinantian of the southern Lake District, UK

Two types of ‘pseudobreccia’, one with grey and the other with brown mottle fabrics, occur in shoaling‐upward cycles of the Urswick Limestone Formation of Asbian (Late Dinantian, Carboniferous) age in the southern Lake District, UK. The grey mottle pseudobreccia occurs in cycle‐base packstones and developed after backfilling and abandonment of Thalassinoides burrow systems. Burrow infills consist of a fine to coarse crystalline microspar that has dull brown to moderate orange colours under cathodoluminescence. Mottling formed when an early diagenetic ‘aerobic decay clock’ operating on buried organic material was stopped, and sediment entered the sulphate reduction zone. This probably occurred during progradation of grainstone shoal facies, after which there was initial exposure to meteoric water. Microspar calcites then formed rapidly as a result of aragonite stabilization. The precipitation of the main meteoric cements and aragonite bioclast dissolution post‐date this stabilisation event. The brown mottle pseudobreccia fabrics are intimately associated with rhizocretions and calcrete, which developed beneath palaeokarstic surfaces capping cycle‐top grainstones and post‐date all depositional fabrics, although they may also follow primary depositional heterogeneities such as burrows. They consist of coarse, inclusion‐rich, microspar calcites that are always very dull to non‐luminescent under cathodoluminescence, sometimes with some thin bright zones. These are interpreted as capillary rise and pedogenic calcrete precipitates. The δ¹⁸O values (?5‰ to ?8‰, PDB) and the δ¹³C values (+2‰ to ?3‰, PDB) of the ‘pseudobreccias’ are lower than the estimated δ¹⁸O values (?3‰ to ?1‰ PDB) and δ¹³C values of (+2‰ to +4‰ PDB) of normal marine calcite precipitated from Late Dinantian sea water, reflecting the influence of meteoric waters and the input of organic carbon.     

Nodular celestite in the Chihsia Formation (Middle Permian) of south China

The middle Permian Chihsia Formation of south China accumulated on a shallow shelf, and consists mainly of black to dark grey micritic limestone rich in chert nodules and organic matter. A unique type of nodular crystal cluster is distributed widely in the carbonate succession. Most crystal clusters consist of calcite. Some, however, are composed of celestite, and geochemical, microscopic and crystal morphological data suggest that celestite was the precursor of the calcite. The celestite developed displacively within the sediments during early diagenesis, before compaction and before local dolomitization of the host rock. Similar strontium isotopic values were obtained from the celestite clusters, replacement calcite, vein calcite and host rock. The values are within the range of middle Permian sea water. The strontium in the celestite was furnished chiefly by either diagenetic alteration of strontium‐rich marine aragonite to strontium‐poor calcite, or aragonite dissolution induced by aerobic oxidation of organic matter, or both. The sulphur isotopic values of the celestite are about 6–11‰ heavier than the sulphur isotopic value of sulphate in coeval sea water. Based on geological context, this difference is attributed to microbial reduction of porewater sulphate in the Chihsia sediments.     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

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.     

Aragonite and calcite preservation in sediments from Lake Iznik related to bottom lake oxygenation and water column depth

This study examines the forcing mechanisms driving long‐term carbonate accumulation and preservation in lacustrine sediments in Lake Iznik (north‐western Turkey) since the last glacial. Currently, carbonates precipitate during summer from the alkaline water column, and the sediments preserve aragonite and calcite. Based on X‐ray diffraction data, carbonate accumulation has changed significantly and striking reversals in the abundance of the two carbonate polymorphs have occurred on a decadal time scale, during the last 31 ka cal bp . Different lines of evidence, such as grain size, organic matter and redox sensitive elements, indicate that reversals in carbonate polymorph abundance arise due to physical changes in the lacustrine setting, for example, water column depth and lake mixing. The aragonite concentrations are remarkably sensitive to climate, and exhibit millennial‐scale oscillations. Extending observations from modern lakes, the Iznik record shows that the aerobic decomposition of organic matter and sulphate reduction are also substantial factors in carbonate preservation over long time periods. Lower lake levels favour aragonite precipitation from supersaturated waters. Prolonged periods of stratification and, consequently, enhanced sulphate reduction favour aragonite preservation. In contrast, prolonged or repeated exposure of the sediment–water interface to oxygen results in in situ aerobic organic matter decomposition, eventually leading to carbonate dissolution. Notably, the Iznik sediment profile raises the hypothesis that different states of lacustrine mixing lead to selective preservation of different carbonate polymorphs. Thus, a change in the entire lake water chemistry is not strictly necessary to favour the preservation of one polymorph over another. Therefore, this investigation is a novel contribution to the carbon cycle in lacustrine systems.     

The Holocene non-tropical coastal and shelf carbonate province of southern Australia

Carbonate-dominant sediments are currently forming and accumulating over the extensive marine shelf of the passive margin of southern Australia. A dearth of continental detritus results from both a very low relief and a predominantly arid climate. The wide continental shelf is bathed by cold upwelling ocean waters that support luxuriant growths of bryozoans and coralline algae, together with sponges, molluscs, asteroids, benthic and some planktonic foraminifera. The open ocean coast is battered by a persistent southwest swell, resulting in erosion of calcrete-encrusted Pleistocene eolianites. Much sediment is reworked and overall shelf sedimentation rates are low. High-energy microtidal beach/dune systems occur between headlands and along the very long ocean beach in the Coorong region. The northern, more arid coastal areas also contain saline lakes that precipitate gypsum from infiltrated sea water, and display marginal facies of aragonite boxwork to fenestral carbonate crusts, with stromatolites and tepee structures. In contrast, the southern, seasonally humid Coorong region, has a predominantly continental groundwater regime where sulphate is rare, and the high summer evaporation precipitates dolomite, magnesite and aragonite muds. Fenestral crusts, breccias, tepees and some stromatolites are also present.

St. Vincent and Spencer gulfs both afford some protection from ocean swell, but tidal amplitude and currents increase, and a depth and inundation-related zonation of plants and animals is established. Muddy carbonate sand accumulates on the sea floor below 30 m, where filter-feeding bryozoans, bivalves and sponges dominate. In shallower regions, seagrass meadows contain a rich fauna that results in rapid accumulation of an unsorted muddy bioclastic sand. Mangrove woodlands backed by saline marsh with cyanobacterial mats are common, and accumulate mud-rich and gastropod-bearing sediment. As tidal amplitude and desiccation increase northward into both gulfs, a supratidal zone bare of vegetation (sabkha) becomes the site for deposition of gypsum-rich and fenestral calcitic mud.     

Magnetostratigraphy of the Plio‐Pleistocene carbonate section of the Great Australian Bight

ODP Leg 182 drilled two north‐south transects in the western Great Australian Bight close to longitude 128°E. These transects penetrated a remarkably thick section of uppermost Pliocene and Pleistocene carbonate sediments, which are separated from Miocene sections by a major hiatus. In the eastern transect, at sites 1129, 1131 and 1127, the Brunhes‐Matuyama boundary (onset of C1n) was found at 343 m, between 280 and 300 m, and at 343 m below the sea floor, respectively. In the western transect, at sites 1132 and 1130, it was found between 170 and 181 m, and at 200 m, respectively. Within the Brunhes chron, inclination and intensity fluctuations and correlations between susceptibility and standard δ¹⁸O records were used to give age‐depth relations. These age relations from the palaeomagnetics are broadly consistent with the biostratigraphy and the δ¹⁸O results from Leg 182, but do not provide an entirely independent dataset. Rock magnetism stratigraphy at site 1131 revealed the principal bryozoan buildup to be at the time of the last glacial lowstand, as suggested by previous workers. At all sites the sedimentation rate increases from the basal unconformity up into the thick Upper Pleistocene section. In the western transect there appears to be a partial record of most of the Late Pliocene and Early Pleistocene chron boundaries (C1r1n to C2An3n) in a condensed section, but in the eastern transect only the Jaramillo (C1r1n) is observed.     

Calcium and magnesium‐limited dolomite precipitation at Deep Springs Lake,California

Dolomite [Ca,Mg(CO₃)₂] precipitation from supersaturated ionic solutions at Earth surface temperatures is considered kinetically inhibited because of the difficulties experienced in experimentally reproducing such a process. Nevertheless, recent dolomite is observed to form in hypersaline and alkaline environments. Such recent dolomite precipitation is commonly attributed to microbial mediation because dolomite has been demonstrated to form in vitro in microbial cultures. The mechanism of microbially mediated dolomite precipitation is, however, poorly understood and it remains unclear what role microbial mediation plays in natural environments. In the study presented here, simple geochemical methods were used to assess the limitations and controls of dolomite formation in Deep Springs Lake, a highly alkaline playa lake in eastern California showing ongoing dolomite authigenesis. The sediments of Deep Springs Lake consist of unlithified, clay‐fraction dolomite ooze. Based on δ¹⁸O equilibria and textural observations, dolomite precipitates from oxygenated and agitated surface brine. The Na‐SO₄‐dominated brine contains up to 500 mm dissolved inorganic carbon whereas Mg²⁺ and Ca²⁺ concentrations are ca 1 and 0·3 mm , respectively. Precipitation in the subsurface probably is not significant because of the lack of Ca²⁺ (below 0·01 mm ). Under such highly alkaline conditions, the effect of microbial metabolism on supersaturation by pH and alkalinity increase is negligible. A putative microbial effect could, however, support dolomite nucleation or support crystal growth by overcoming a kinetic barrier. An essential limitation on crystal growth rates imposed by the low Ca²⁺ and Mg²⁺ concentrations could favour the thermodynamically more stable carbonate phase (which is dolomite) to precipitate. This mode of unlithified dolomite ooze formation showing δ¹³C values near to equilibrium with atmospheric CO₂ (ca 3‰) contrasts the formation of isotopically light (organically derived), hard‐lithified dolomite layers in the subsurface of some less alkaline environments. Inferred physicochemical controls on dolomite formation under highly alkaline conditions observed in Deep Springs Lake may shed light on conditions that favoured extensive dolomite formation in alkaline Precambrian oceans, as opposed to modern oceans where dolomites only form diagenetically in organic C‐rich sediments.     

'Forbidden zone' subduction of sediments to 150 km depth— the reaction of dolomite to magnesite + aragonite in the UHPM metapelites from western Tianshan, China

The solid‐state reaction magnesite (MgCO₃) + calcite (aragonite) (CaCO₃) = dolomite (CaMg(CO₃)₂) has been identified in metapelites from western Tianshan, China. Petrological studies show that two metamorphic stages are recorded in the metapelites: (1) the peak mineral assemblage of magnesite and calcite pseudomorphs after aragonite which is only preserved as inclusions within dolomite; and (2) the retrograde glaucophane‐chloritoid facies mineral assemblage of glaucophane, chloritoid, dolomite, garnet, paragonite, chlorite and quartz. The peak metamorphic temperatures and pressures are calculated to be 560–600 °C, 4.95–5.07 GPa based on the calcite–dolomite geothermometer and the equilibrium calculation of the reaction dolomite = magnesite + aragonite, respectively. These give direct evidence in UHP metamorphic rocks from Tianshan, China, that carbonate sediments were subducted to greater than 150 km depth. This UHP metamorphism represents a geotherm lower than any previously estimated for subduction metamorphism (< 3.7 °C km^?1) and is within what was previously considered a ‘forbidden’ condition within Earth. In terms of the carbon cycle, this demonstrates that carbonate sediments can be subducted to at least 150 km depth without releasing significant CO₂ to the overlying mantle wedge.     

Changes in carbon and oxygen isotope composition during limestone diagenesis

The calcite fossils of the Derbyhaven Beds, Isle of Man, have δ¹³C values (+ 1·8 PDB) similar to modern, shallow-water marine skeletons, but the δ¹⁸O values (?6·1 PDB) are much lighter than modern skeletons. The light oxygen values indicate either re-equilibration with isotopically light water before cementation started, or Carboniferous sea water with δ¹⁸O of ?6‰. Aragonite dissolution was followed by precipitation of zoned calcite cement. In this cement, up to six intracrystalline zones, recognized in stained thin sections, show isotopic variation. Carbon varies from + 3-8 to + 1-2‰. and oxygen from ? 2-6 to ? 12-4‰. with decreasing age of the cement. This trend is attributed to increasing temperature and to isotopic evolution of the pore waters during burial. The zoned calcite is sequentially followed by dolomite and kaolinite cements which continue the trend towards light isotopic values. This trend is continued with younger, fault-controlled dolomite, and is terminated by vein-filling calcite and dolomite. The younger calcite, interpreted as a near-surface precipitate from meteoric waters, is unrelated to the older sequence of carbonates and has distinctly different carbon isotope ratios: δ¹³C ? 6-8‰.     

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.     

Eocene cool-water carbonate and biosiliceous sedimentation dynamics, St Vincent Basin, South Australia

Middle and Upper Eocene biogenic sediments in the Willunga Embayment along the eastern margin of the St Vincent Basin are a series of warm‐temperate limestones, marls and spiculites. The Middle Eocene Tortachilla Limestone is a thin, coarse grained, quartzose, biofragmental, bryozoan–mollusc calcarenite of stacked metre‐scale depositional cycles with hardground caps. Lithification, aragonite dissolution and the filling of moulds by sediment and cement characterize early marine‐meteoric diagenesis. Further meteoric diagenesis at the end of Tortachilla deposition resulted in dissolution, Fe‐oxide precipitation and calcite cementation. The Upper Eocene Blanche Point Formation is composed of coccolith and spiculite marl and spiculite, all locally rich in glauconite, turritellid gastropods and sponges. Decimetre‐scale units, locally capped by firmgrounds, have fossiliferous lower parts and relatively barren upper parts. Carbonate diagenesis is minor, with much aragonite still present, but early silicification is extensive, except in the spiculite, which is still opal‐A. All depositional environments are interpreted as relatively shallow water: high energy during the Middle Eocene and low energy during the Upper Eocene, reflecting the variable importance of a basin‐entrance archipelago of carbonate highs. Marls and spiculites are interpreted to have formed under an overall estuarine circulation system in a humid climate. Basinal waters, although well mixed, were turbid and rich in land‐derived nutrients, yet subphotic near the sea floor. These low‐energy, inner‐shelf biosiliceous sediments occur in coeval environments across other parts of Australia and elsewhere in the rock record, suggesting that they are a recurring element of the cool‐water, carbonate shelf depositional system. Thus, spiculites and spiculitic carbonates in the rock record need be neither deep basinal nor polar in origin. The paradox of a shallow‐water carbonate–spiculite association may be more common in geological history than generally realized and may reflect a characteristic mid‐latitude, humid climate, temperate water, palaeoenvironmental association.     

Stable isotope evidence for the origin of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel

The oxygen isotope compositions of diagenetic carbonate minerals from the Lower Jurassic Inmar Formation, southern Israel, have been used to identify porewater types during diagenesis. Changes in porewater composition can be related to major geological events within southern Israel. In particular, saline brines played an important role in late (Pliocene-Pleistocene) dolomitization of these rocks. Diagenetic carbonates included early siderite (δ¹⁸O_SMOW=+24.4 to +26.5‰δ¹³C_PDB=?1.1 to +0.8‰), late dolomite, ferroan dolomite and ankerite (δ¹⁸O_SMOW=+18.4 to +25.8‰; δ¹³C_PDB=?2.1 to +0.2‰), and calcite (δ¹⁸O_SMOW=+21.3 to +32.6‰; δ¹³C_PDB=?4.2 to + 3.2‰). The petrographic and isotopic results suggest that siderite formed early in the diagenetic history at shallow depths. The dolomitic phases formed at greater depths late in diagenesis. Crystallization of secondary calcite spans early to late diagenesis, consistent with its large range in isotopic values. A strong negative correlation exists between burial depth (temperature) and the oxygen isotopic compositions of the dolomitic cements. In addition, the δ¹⁸O values of the dolomitic phases in the northern Negev and Judea Mountains are in isotopic equilibrium with present formation waters. This behaviour suggests that formation of secondary dolomite post-dates the tectonic activity responsible for the present relief of southern Israel (Upper Miocene to Pliocene) and that the dolomite crystallized from present formation waters. Such is not the case in the Central Negev. In that locality, present formation waters have much lower salinities and δ¹⁸O values, indicating invasion of freshwater, and are out of isotopic equilibrium with secondary dolomite. Recharge of the Inmar Formation by meteoric water in the Central Negev occurred in the Pleistocene, and halted formation of dolomite.