衡阳盆地始新世含鱼地层的成因分析

衡阳市郊五马归槽始新世鱼化石保存在黑色湖相纹层中。根据纹层序列的对比,发现该地的鱼化石均为同一层位;根据鱼化石在纹层序列中的具体位置及鱼化石的保存状况,笔者推测鱼群的死亡并非由于季节更替,而是由气候干旱引起的湖水盐度升高所控制;黑白纹层的变化是由大气降雨所致。     

Advances in understanding calcite varve formation: new insights from a dual lake monitoring approach in the southern Baltic lowlands

We revise the conceptual model of calcite varves and present, for the first time, a dual lake monitoring study in two alkaline lakes providing new insights into the seasonal sedimentation processes forming these varves. The study lakes, Tiefer See in NE Germany and Czechowskie in N Poland, have distinct morphology and bathymetry, and therefore, they are ideal to decipher local effects on seasonal deposition. The monitoring setup in both lakes is largely identical and includes instrumental observation of (i) meteorological parameters, (ii) chemical profiling of the lake water column including water sampling, and (iii) sediment trapping at both bi-weekly and monthly intervals. We then compare our monitoring data with varve micro-facies in the sediment record. One main finding is that calcite varves form complex laminae triplets rather than simple couplets as commonly thought. Sedimentation of varve sub-layers in both lakes is largely dependent on the lake mixing dynamics and results from the same seasonality, commencing with diatom blooms in spring turning into a pulse of calcite precipitation in summer and terminating with a re-suspension layer in autumn and winter, composed of calcite patches, plant fragments and benthic diatoms. Despite the common seasonal cycle, the share of each of these depositional phases in the total annual sediment yield is different between the lakes. In Lake Tiefer See calcite sedimentation has the highest yields, whereas in Lake Czechowskie, the so far underestimated re-suspension sub-layer dominates the sediment accumulation. Even in undisturbed varved sediments, re-suspended material becomes integrated in the sediment fabric and makes up an important share of calcite varves. Thus, while the biogeochemical lake cycle defines the varves’ autochthonous components and micro-facies, the physical setting plays an important role in determining the varve sub-layers’ proportion.     

Precambrian non-marine stromatolites in alluvial fan deposits, the Copper Harbor Conglomerate, upper Michigan

Laminated cryptalgal carbonates occur in the Precambrian Copper Harbor Conglomerate of northern Michigan, which was deposited in the Keweenawan Trough, an aborted proto-oceanic rift. This unit is composed of three major facies deposited by braided streams on a large alluvial-fan complex. Coarse clastics were deposited in braided channels, predominantly as longitudinal bars, whereas cross-bedded sandstones were deposited by migrating dunes or linguoid bars. Fine-grained overbank deposits accumulated in abandoned channels. Gypsum moulds and carbonate-filled cracks suggest an arid climate during deposition. Stromatolites interstratified with these clastic facies occur as laterally linked drapes over cobbles, as laterally linked contorted beds in mudstone, as oncolites, and as poorly developed mats in coarse sandstones. Stromatolites also are interbedded with oolitic beds and intraclastic conglomerates. Stromatolitic microstructure consists of alternating detrital and carbonate laminae, and open-space structures. Radial-fibrous calcite fans are superimposed on the laminae. The laminae are interpreted as algal in origin, whereas the origin of the radial fibrous calcite is problematic. The stromatolites are inferred to have grown in lakes which occupied abandoned channels on the fan surface. Standing water on a permeable alluvial fan in an arid climate requires a high water table maintained by high precipitation, or local elevation of the water table, possibly due to the close proximity of a lake. Occurrence of stromatolites in the upper part of the Copper Harbor Conglomerate near the base of the lacustrine Nonesuch Shale suggests that these depositional sites may have been near the Nonesuch Lake.     

Saline lake carbonates within an Upper Jurassic-Lower Cretaceous continental red bed sequence in the Atacama region of northern Chile

The Codocedo Limestone Member is a thin but laterally persistent lacustrine sequence within the red beds of the Upper Jurassic-Lower Cretaceous Quebrada Monardes Formation, in the Atacama region of northern Chile. The thick succession of clastic terrigenous sediments of the Quebrada Monardes Formation was deposited in an arid to semi-arid environment. Sedimentary facies are indicative of deposition of aeolian dunes, alluvial fans and braided streams, playa-lake mudflats, and saline lakes and coastal lagoons. The strata accumulated in a N-S elongated extensional back-arc basin on the landward side of an active volcanic arc. The 3 m thick Codocedo Limestone Member marks striking facies changes within the Quebrada Monardes Formation. It is underlain by a thick sequence of conglomerates and sandstones, deposited on alluvial fans. The limestone itself is characterized by evaporite minerals and laterally continuous laminations, indicative of deposition by vertical accretion in a perennial saline lake. The overlying siltstones and fine sandstones contain geodes and gypsum pseudomorphs and were deposited on playa-lake mudflats. The limestone therefore represents a relatively short period of lacustrine deposition within an essentially terrigenous succession. The lake was possibly formed quite suddenly, for example by damming of the basin by a lava flow. Sedimentation in the perennial lake was predominantly cyclical. Seasonal planktonic algal blooms produced millimetre-scale laminations. Interbedded with these laminites are centimetre-scale beds of evaporitic gypsum, anhydrite and minor halite. The evaporite minerals have been largely replaced by calcite, chalcedony and quartz. The centimetre-scale cycles may have resulted from periodic freshwater input into the lake. After a period of about 3000 yr the lake dried up, to be replaced by extensive playa-lake mudflats. The Codocedo Limestone Member possibly formed a plane of detachment during an early Tertiary phase of E-W directed regional compression. The limestones and evaporites were folded and extensively brecciated. This deformation probably resulted from simple shear along the bedding plane of the relatively weak evaporite minerals prior to their replacement by calcite and quartz.     

Sedimentology of the Cretaceous Maha Sarakham evaporites in the Khorat Plateau of northeastern Thailand

Evaporites of the Cretaceous to early Tertiary Maha Sarakham Formation on the Khorat Plateau of southeast Asia (Thailand and Laos) are composed of three depositional members that each include evaporitic successions, each overlain by non-marine clastic red beds, and are present in both the Khorat and the Sakon Nakhon sub-basins. These two basins are presently separated by the northwest-trending Phu Phan anticline. The thickness of the formation averages 250 m but is up to 1.1 km thick in some areas. In both basins it thickens towards the basin centre suggesting differential basin subsidence preceding or during sedimentation. The stratigraphy, lithological character and mineralogy of the evaporites and clastics are identical in both basins suggesting that they were probably connected during deposition. Evaporites include thick successions of halite, anhydrite and a considerable accumulation of potassic minerals (sylvite and carnallite) but contain some tachyhydrite, and minor amounts of borates. During the deposition of halite the basin was subjected to repeated inflow of fresher marine water that resulted in the formation of anhydrite marker beds. Sedimentary facies and textures of both halite and anhydrite suggest deposition in a shallow saline-pan environment. Many halite beds, however, contain a curious `sieve-like' fabric marked by skeletal anhydrite outlines of gypsum precursor crystals and are the product of early diagenetic replacement by halite of primary shallow-water gypsum. The δ³⁴S isotopic values obtained from different types of anhydrite interbedded with halite range from 14.3‰ to 17.0‰ (CDT), suggesting a marine origin for this sulphate. Bromine concentration in the halite of the Lower Member begins around 70 ppm and systematically increases upward to 400 ppm below the potash-rich zone, also suggesting evaporation of largely marine waters. In the Middle Member the initial concentration of bromine in halite is 200 ppm, rising to 450 ppm in the upper part of this member. The bromine concentration in the Upper Member exhibits uniform upward increase and ranges from 200 to 300 ppm. The presence of tachyhydrite in association with the potassic salts was probably the result of: (1) the large volumes of halite replacement of gypsum, on a bed by bed basis, releasing calcium back into the restricted waters of the basin; and (2) early hydrothermal input of calcium chloride-rich waters. The borates associated with potash-rich beds likely resulted from erosion and influx of water from surrounding granitic terrains; however, hydrothermal influx is also possible. Interbedded with the evaporites are non-marine red beds that are also evaporative, with displacive anhydrite nodules and beds and considerable amounts of displacive halite. The δ³⁴S isotopic values of this anhydrite have non-marine values, ranging from 6.4‰ to 10.9‰ (CDT). These data indicate that the Khorat and Sakhon Nakhon basins underwent periods of marine influx due to relative world sea-level rise but were sporadically isolated from the world ocean.     

Mineral equilibria in a six-component seawater system,Na-K-Mg-Ca-SO4-Cl-H2O,at 25°C

Phase relations in the 6-component system Na-K-Mg-Ca-SO₄-Cl-H₂O have been calculated for halite saturation, 25°C and 1 atm pressure. Using a Jänecke projection with the apices Ca-Mg-K₂-SO₄, 27 stable invariant points have been located which are connected by 69 univariant curves. Polyhalite is the only quaternary solid, but anhydrite occupies the bulk of the interior tetrahedral space. Consequently, 24 of the invariant points lie very close to the Ca-free base, Mg-K₂-SO₄. The remaining three points involve tachyhydrite and/or antarcticite. All points but two (20,27) represent peritectic conditions. Metastable equilibria have been calculated for the Ca-free system and yield relations corresponding to the solar diagram.Seawater lies in the subspace anhydrite-halite-carnallite-kieserite-bischofite (point 20) and its evaporation has been discussed for conditions of equilibrium and fractional crystallization. After gypsum is converted to anhydrite, halite precipitates. The next phase, under equilibrium conditions, is glauberite, crystallizing at the expense of anhydrite. Continued evaporation leads to glauberite resorption and eventual replacement by polyhalite. Then follow the magnesium sulfates epsomite, hexahydrite and kieserite, which are joined by carnallite. Polyhalite is replaced by anhydrite and bischoflte is added at the final invariant condition. Kainite does not appear as a primary phase under equilibrium conditions, but it is an important phase during fractional crystallization, where Ca-phases are not allowed to back-react with the brine.Up to the appearance of glauberite, thickness ratios of halite: anhydrite couplets (equilibrium or fractionation) can vary from 0 to 7, the relative amount of halite increasing with more intense evaporation. During evaporation, the activity of H₂O decreases from 0.98 (seawater) to 0.34 (final invariant brine). The data provided can be used to evaluate the effects of mineral precipitation, evaporation and brine mixing for a wide variety of natural brines.     

室温条件下青海湖水中镁离子浓度对沉淀碳酸钙同质多像类型的调控

青海湖是我国唯一报道过的现代湖底沉积物中白云石、方解石和文石等多种碳酸盐矿物共存的高原内陆咸水湖泊。以青海湖水和除菌青海湖水作为载体,以CaCl_2和MgCl_2·6 H_2O作为反应原料,在实验室常温条件下采取控制变量法制备出不同浓度Mg~(2+)参与下的钙质沉淀物,探讨Mg~(2+)浓度对沉淀物类型的影响。仅添加CaCl_2时,青海湖水中的沉淀物主要是石膏(Ca SO_4·2 H_2O)和球霰石(CaCO_3);在添加CaCl_2的同时添加MgCl_2·6 H_2O,沉淀物的石膏消失,完全转变成碳酸盐矿物,包括方解石和球霰石;当湖水中Mg~(2+)浓度为0.62 mol/L时,球霰石消失,沉淀物变为方解石和文石;随着Mg~(2+)浓度继续升高,文石含量稳步增加,方解石含量则逐渐减少,当Mg~(2+)浓度达到1.22 mol/L或更高时,方解石全部消失,沉淀物仅剩文石。实验结果表明,青海湖水中较高浓度的SO_4~(2-)对碳酸钙晶体生长有抑制作用,而额外加入的Mg~(2+)可以解除SO_4~(2-)的抑制作用,使得Ca~(2+)与HCO_3~-和CO_3~(2-)结合形成碳酸钙。此外,碳酸钙的同质多像类型也明显受到Mg~(2+)浓度的控制,随着湖水中Mg~(2+)浓度增加,方解石、球霰石不再稳定,而文石逐渐占主导地位,当Mg/Ca值达到6.1时,反应产物中仅有文石稳定存在。     

Centennial-scale oscillations in oxygen and carbon isotopes of endogenic calcite from a 15,500 varve year record of the Piànico interglacial

The palaeolake record from Piànico (Southern Alps) comprises a sequence of 15,500 continuous calcite varves formed during peak interglacial conditions around 400 ka ago. The varved nature of these deposits allows precise sub-sampling of five varve year intervals for stable isotope analyses. All samples consist of calcite precipitated in the epilimnion of the lake, with contents of detrital carbonate below 4%. Four significant negative δ¹⁸O oscillations occurred during the upper half of the interglacial. The most prominent of these oscillations has an amplitude of −1.1‰ and lasted 780 varve years. The three other oscillations are shorter (125–195 varve years) and of lower amplitude (0.4–0.9‰). An additional major drop in δ¹⁸O occurs 315 varve years before the end of continuous calcite precipitation in the lake. This shift marks the end of long interglacial conditions and the beginning of harsher climate conditions and glacier advances in the Southern Alps. In contrast, the four δ¹⁸O oscillations within the period of continuous formation of calcite varves reflect natural intra–interglacial climate dynamics.     

Mineralogy,diagenesis and hydrochemical evolution in a probertite–glauberite–halite saline lake (Miocene,Emet Basin,Turkey)

The Emet basin is one of the Neogene basins in western Turkey containing significant amounts of borate minerals, mainly colemanite. The petrologic study of core samples from two exploratory wells in the Do?anlar sector, under optic and electron microscopy, reveals a complex mineral association in which probertite, glauberite, and halite constitute the major primary phases (without mineral precursors) precipitated in a saline lake placed in a volcano-sedimentary context. Other sulfates (anhydrite, gypsum, thenardite, celestite and kalistrontite), borates (colemanite, ulexite, hydroboracite, tunellite, kaliborite and aristarainite), and sulfides (arsenopyrite, realgar and orpiment) are attributed to early diagenesis. So far, the Do?anlar deposit is the most important deposit of probertite known up to now.Chemical changes in the groundwater inflow led to the precipitation of Ca-bearing borates (colemanite) in the tuff-flat environment surrounding the lake, while Na–Ca sulfates and borates (glauberite and probertite) precipitated in the center of the lake. Fluid inclusion compositions in halite indicate that the advanced brines correspond to the Na-K-Cl-SO₄ type. During restricted stages of the saline lake, the residual brines seeped through the tuff-flat sediments, leading to transformations of previous precipitates that resulted in the formation of K-bearing minerals.The abundance of coccoid-like biogenic dolomite, colloidal arsenopyrite and the isotopic composition of sulfates are indicative of bacterial sulfate reduction. In contrast, arsenic sulfides are attributed to acidophilic micro-organisms in oxidizing conditions. Fluctuations of redox conditions in both free and interstitial brines control the biological influence in some diagenetic transformations.     

Global Radiation and Onset of Stratification as Forcing Factors of Seasonal Carbonate and Organic Matter Flux Dynamics in a Hypertrophic Hardwater Lake (Sacrower See,Northeastern Germany)

A 2-year (October 2003–October 2005) high-resolution sediment trap study was conducted in Sacrower See, a dimictic hardwater lake in northeastern Germany. Geochemical and diatom data from sediment trap samples were compared with a broad range of limnological and meteorological parameters to quantify the impact of single parameters on biochemical calcite precipitation and organic matter production. Our goals were to disentangle how carbonaceous varves and their sublaminae form during the annual cycle to better understand the palaeorecords and to detect influences of dissolution, resuspension as well as of global radiation and stratification on lake internal particle formation. Total particle fluxes in both investigated years were highest during spring and summer. Sedimentation was dominated by autochthonous organic matter and biochemically precipitated calcite. Main calcite precipitation occurred between April and July and was preceded and followed by smaller flux peaks caused by resuspension during winter and blooms of the calcified green algae Phacotus lenticularis during summer. In some of the trap intervals during summer up to 100% of the precipitated calcite was dissolved in the hypolimnion. High primary production due to stable insolation conditions in epilimnic waters began with stratification of the water column. Start and development of stratification is closely related to air and water surface temperatures. It is assumed that global radiation influences the onset and stability of water column stratification and thereby determining the intensity of primary production and consequently of timing and amount of calcite precipitation which is triggered by phytoplanktonic CO₂ consumption. Sediment fluxes of organic matter and calcite are also related to the winter NAO-Index. Therefore these fluxes will be used as a proxy for ongoing reconstruction of Holocene climate conditions.     

A thermodynamic model for the prediction of phase equilibria and speciation in the H2O-CO2-NaCl-CaCO3-CaSO4 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to halite saturation

A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H₂O-CO₂-NaCl-CaCO₃-CaSO₄ system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H⁺,Na⁺,Ca²⁺, , , and CaSO_4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results.Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO₂ in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model.     

Sedimentation rates in Fayetteville Green Lake, New York, U.S.A.

In Fayetteville Green Lake, past sedimentation rates can be accurately and precisely estimated by separating annual couplets or varves in dried sediment samples. Two measures were used, which serve as upper and lower limits on estimated sedimentation rate. They agree within 5 % with average annual sedimentation rate in couplets for recent years. Between 3 and 5 replicate samples are needed to reduce the half-width of 95 % confidence intervals on individual couplet sedimentation rates to 30 g m^?2 yr^?1 about 5 % of average recent rates. In the late 1800s sedimentation rate averaged 392 g m^?2 yr^?1 and ranged between 324 and 466 g m^?2 yr^?1, while in the 1970s the rate averaged 581 g m^?2 yr^?1 by the same measure, and ranged between 384 and 646 g m^?2 yr^?1. Sedimentation rate averaged for 13 years does not vary over short distances in the profundal zone, but lateral variation in sedimentation rate can be detected for individual years over the same distance. Not all this variation was associated with the non-uniform distribution of dark sublaminae and thin turbidites which cannot be separated from the annual layers. This indicates that although precise estimates of sedimentation rates can be made at different points in the lake, estimates will have to be made at numerous points before annual sedimentation rates for the lake as a whole can be accurately assessed.     

Sedimentological and geochemical evidence to elucidate an evaporitic–carbonate paleoenvironment, Middle Miocene Red Sea coast, Egypt

Lithologic succession, microscopic examination as well as X-ray diffraction and chemical data revealed that the surface Middle Miocene evaporites of Wadi Quei are composed of anhydrite beds intercalated with carbonate and green shale, whilst the subsurface evaporites of Gemsa locality are composed of gypsum, anhydrite, carbonates and celestite with a rare amount of halite. The anhydrite is found to be formed diagenetically after gypsum. The carbonate is interpreted as having been of biogenic origin. The strong smell of H₂S and golden crystals of pyrite at Wadi Quei beds are indications of the biogenic action of sulphate-reducing bacteria in the presence of organic matter. It is suggested that the evaporite sequence which was deposited in a supratidal sabkha environment is characterized by alkaline-reducing conditions. The presence of nodular gypsum at Gemsa locality is probably deposited in a supratidal environment with oscillation of sea level.     

Calcite from the Quaternary spring waters at Tylicz, Krynica, Polish Carpathians

At Tylicz, near Krynica Spa (Polish Carpathians), spelean deposits fill fissures and caverns in Eocene flysch rocks. They occur as: (1) clastic cave sediments transformed into hard crusts due to cementation by finely crystalline low-Mg calcite, (2) drusy calcite that covers crust surfaces and fills voids in the crust and (3) colloform calcite. Two varieties of drusy calcite are distinguished: acicular and columnar. The acicular calcite is built up of crystallites forming spherulitic fans or cones. In places it is syntaxially covered with colloform calcite. The drusy calcite is low-Mg ferroan calcite with non-ferroan subzones, whereas the colloform calcite is a low-Mg non-ferroan variety. The columnar calcite crystals form fan-like bundles. Cross-sections cut perpendicular to the c-axes of columnar crystals are equilateral triangular in shape, although some have slightly curved edges. The columnar crystals have steep rhombic terminations and most have curved triangular faces, i.e. gothic-arch calcite. Saddle crystals have also been observed. The columnar crystals are composed of radially orientated crystallites whose long dimension is parallel to the c-axis. The curved crystal faces of such polycrystals are interpreted as a result of differential growth rates of the crystallites. The spelean calcites precipitated from CO₂-saturated water. The high rate of CaCO₃ precipitation is thought to be responsible for the formation of radial structures. Finely crystalline calcite formed within pore spaces of clastic sediments close to the water-air interface, drusy calcite crystallized beneath the water-air interface, and colloform calcite precipitated from thin films of water.     

Sedimentology and evaporite genesis in a Holocene continental-sabkha playa basin—Bristol Dry Lake, California

Bristol Dry Lake, a 155 km² continental-sabkha playa basin in the Mojave Desert of south eastern California, is filled with at least 300 m of interbedded terrigenous clastics, gypsum, anhydrite, and halite. Evaporite facies conform approximately to a bull's eye pattern with gypsum and anhydrite surrounding a basin centre accumulation of halite. Transects through Bristol Dry Lake, from the alluvial fan to the centre of the playa, reveal: (1) crudely-bedded, alluvial fan clastics interfingering with (2) playa-margin sand flat and wadi sand and silt, followed by (3) gypsum, anhydrite, chaotic mud halite, and clay of the saline mud flat, and (4) salt-pan halite beds. Terrigenous clastics were deposited in Bristol Dry Lake by sheetflow and by suspension settling from ponded floodwater. Some sediment has been reworked by aeolian processes to form barchan dunes around the playa margin. Thin nodular-like beds of anhydrite and several types of gypsum occur across most of the playa. Giant hopper-shaped halite cubes are suspended in saline mud flat facies, suggesting that they grew displacively in brine soaked sediment just below the surface. Thick beds (4 m) of halite, in the playa centre, may have formed through a complex alternating history of subaqueous and intrasedimentary precipitation under the influence of periodic floods, intense evaporation and brine-level lowering, and capillary discharge of brines. The stratigraphy in the playa centre is cyclic. An ideal cycle consists of: (1) chaotic mud halite at the base overlain by (2) green to red clay with abundant, giant hoppers, and at the top (3) red clay, gypsum, and anhydrite with flaser- to wavy-bedded sand and silt. This type of cycle probably records a gradual progradation of mud-flat facies over salt pans. Bristol Dry Lake sediments are nearly identical to some of the Permian evaporites of the Permian Basin region, U.S.A. and they can serve as modern analogues for ancient-sabkha facies analysis.     

Precipitation of amorphous CaCO3 (aragonite-like) by cyanobacteria: A STXM study of the influence of EPS on the nucleation process

An amorphous or nanocrystalline calcium carbonate (ACC) phase with aragonite-like short-range order was found to be a transient precursor phase of calcite precipitation mediated by cyanobacteria of the strain Synechococcus leopoliensis PCC 7942. Using scanning transmission X-ray microscopy (STXM), different Ca-species such as calcite, aragonite-like CaCO₃, and Ca adsorbed on extracellular polymers were discriminated and mapped, together with various organic compounds, at the 30 nm-scale. The nucleation of the amorphous aragonite-like CaCO₃ was found to take place within the tightly bound extracellular polymeric substances (EPS) produced by the cyanobacteria very close to the cell wall. The aragonite-like CaCO₃ is a type of ACC since it did not show either X-ray or electron diffraction peaks. The amount of aragonite-like CaCO₃ precipitated in the EPS was dependent on the nutrient supply during bacterial growth. Higher nutrient concentrations (both N and P) during the cultivation of the cyanobacteria resulted in higher amounts of precipitation of the aragonite-like CaCO₃, whereas the amount of Ca²⁺ adsorbed per volume of EPS was almost independent of the nutrient level. After the onset of the precipitation of the thermodynamically stable calcite and loss of supersaturation the aragonite-like CaCO₃ dissolved whereas Ca²⁺ remained sorbed to the EPS albeit at lower concentrations. Based on these observations a model describing the temporal and spatial evolution of calcite nucleation on the surface of S. leopoliensis was developed. In another set of STXM experiments the amount of aragonite-like CaCO₃ precipitated on the cell surface was found to depend on the culture growth phase: cells in the exponential growth phase adsorbed large amounts of Ca within the EPS and mediated nucleation of ACC, while cells at the stationary/death phase neither adsorbed large amounts of Ca²⁺ nor mediated the formation of aragonite-like CaCO₃. It is suggested that precipitation of an X-ray amorphous CaCO₃ layer by cyanobacteria could serve as a protection mechanism against uncontrolled precipitation of a thermodynamically stable phase calcite on their surface.     

A barred-basin marine evaporite in the Upper Proterozoic of the Amadeus Basin, central Australia

The Ringwood evaporite is part of the 900 m.y. old Bitter Springs Formation, a warm-water shallow-marine sequence of stromatolitic dolomite and limestone, microfossiliferous chert, red beds, quartzite, and evaporites. The evaporite at Ringwood comprises two parts: (i) a lower 127 m characterized by brecciated pyritic bituminous dolomite, together with smaller amounts of dolomite-gypsum breccia, friable chloritic dololutite, coarsely crystalline anhydrite, and satin-spar gypsum; and (ii) an upper 133 m which is similar except that bituminous dolomite forms only one bed, and the characteristic rock-type is dolomite-gypsum breccia. The evaporite is overlain by limestone breccia and massive stromatolitic limestone, interpreted as an algal reef. Gypsum is secondary after anhydrite, and the ratio of gypsum to anhydrite increases upwards. The evaporite shows none of the features of a sabkha or desiccated deep ocean basin deposit, and instead is interpreted as the filling of a barred basin which was cut off from the ocean by growth of an algal barrier reef. As circulation became restricted, bituminous dolomite deposited in the lagoon behind the reef, together with pyrite from the destruction by anaerobic bacteria of algal debris derived from the reef. With continued evaporation, brine concentration increased and gypsum precipitated. Occasional dust storms contributed wind-blown clay to the deposit. The barrier reef transgressed diachronously across the evaporite lagoon, and was eventually drowned when normal marine conditions became established. Burial of the evaporite to about 7000 m beneath the succeeding sediments of the Amadeus Basin converted gypsum to anhydrite, and formed chlorite by reaction of clay with dolomite. Late Palaeozoic tectonism folded and brecciated the rocks, and was followed by erosion which eventually exposed the evaporite to ingress of meteoric water. Hydration of anhydrite to gypsum ensued, the reaction becoming less complete with increasing depth from the ground surface.     

Dolomitization and the mineralization of the Marl Slate (N. E. England)

The Marl Slate, the English equivalent of the Kupferschiefer, has been studied with particular reference to the relationships between dolomitization and the origin of the metal sulphides. Dolomite occurs as: 1) discontinuous lenses of ferroan dolomicrite, 2) micronodules of finely crystalline dolospar in association with length-slow chalcedony and 3) discrete laminae of ferroan or non-ferroan dolospar. The ferroan dolomicrite has excess CaCO₃, and is more abundant in the lower, sapropelic facies of the Marl Slate. It is considered to have formed by the penecontemporaneous alteration of calcium carbonate under hypersaline conditions. Small micronodules (typically about 0.3 mm in diameter) are also more abundant in the sapropelic Marl Slate. These frequently contain cores of length-slow chalcedony (quartzine) fibres and sometimes quartz megacrysts. Textural observations clearly indicate that this silica is of authigenic origin and the dolomite/chalcedony micronodules are interpreted as diagenetic replacements of a calcium sulphate mineral such as anhydrite. The discrete laminae of finely crystalline dolospar are often inter-laminated with calcite in the upper part of the Marl Slate. This dolomite is also calcium rich and represents a replacement, possibly of anhydrite, during a later phase of diagenesis. Metal sulphides occur in two distinct forms: as disseminated framboidal pyrite and as discrete lenses of pyrite, chalcopyrite, galena, sphalerite and rarer sulphides. The framboidal pyrite originated during early diagenesis by reaction of sulphide, produced by reduction of sulphate by organic material and micro-organisms, with iron also released in the reducing environment. The sulphide lenses are often in intimate association with dolospar, length-slow chalcedony and authigenic quartz megacrysts. This indicates that the lenses were produced during diagenesis by the reduction and replacement of calcium sulphate (anhydrite). Various sources, such as co-precipitation with dolomite precursors and the underlying Yellow Sands, may have supplied metals which were mobilized and transported by connate brines as diagenesis progressed.     

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.