Microbially mediated dolomite in Cambrian stromatolites from the Tarim Basin,north‐west China: implications for the role of organic substrate on dolomite precipitation

Dolomite [CaMg(CO₃)₂] is abundant in sedimentary rocks throughout the geological record, but it is rarely found in modern sediments. Also, it cannot be precipitated under low‐temperature conditions in the laboratory without microbial mediation and, as a result, its origin remains a long‐standing enigma. This study reports biologically mediated dolomite precipitation in ancient microbial mats and biofilms from the Cambrian Tarim Basin. The ambient temperature at the time of dolomite precipitation was estimated from δ¹⁸O values from early diagenetic dolomite, and the presence of structures associated with extracellular polymeric substances (EPS), is composed of fibres arranged in a reticular pattern, would favour epitaxial crystallization of dolomite on an organic substrate. In addition, poorly crystallized dolomite formed nanocrystal aggregates that strongly resemble the morphology and size distribution observed in microbial culture experiments. These lines of evidence confirm that microbial structures can be preserved in ancient dolomite and validate their use as biosignatures.     

Characterization of the Microbial Dolomite of the Upper Sinian Dengying Formation in the Hanyuan Area of Sichuan Province, China

The algal dolostone of the Upper Sinian Dengying Formation (corresponding to the Ediacaran system) in the Upper Yangtze Platform of China possesses a rich diversity of microorganisms and is an ideal site for the study of ancient microbial dolomite. We focused on algal dolostone and its microbial dolomite in the Hanyuan area of Sichuan Province, China. The macroscopic petrological features, microscopic morphology, texture characteristics of the fossil microorganisms and microbial dolomite, and geochemical characteristics were investigated. We found rich fossil microorganisms and microbial dolomites in the laminated, stromatolithic, uniform and clotted (algal) dolostones. The microorganisms present were mainly body fossils of cyanobacteria (including Renalcis, Girvanella, Nanococcus, and Epiphyton) and their trace fossils (including microbial mats (biofilms), algal traces, and spots). In addition, there was evidence of sulfate-reducing bacteria (SRB), moderately halophilic aerobic bacteria, and red algae. The microbial dolomites presented cryptocrystalline textures under polarizing microscope and nanometer-sized granular (including spherulitic and pene-cubical granular) and (sub) micron-sized sheet-like, irregular, spherical and ovoidal morphologies under scanning electron microscope (SEM). The microbial dolomites were formed by microbially induced mineralization in the intertidal zone and lagoon environments during the depositional and syngenetic stages and microbially influenced mineralization in the supratidal zone environment during the penecontemporaneous stage. The microbial metabolic activities and extracellular polymeric substances (EPS) determined the morphology and element composition of microbial dolomite. During the depositional and syngenetic stages, the metabolic activities of cyanobacteria and SRB were active and EPS, biofilms and microbial mats were well-developed. EPS provided a large number of nucleation sites. Accordingly, many nanometer-sized pene-cubical granular and (sub) micron-sized sheet-like microbial dolomites were formed. During the penecontemporaneous stage, SBR, cyanobacteria, and moderately halophilic aerobic bacteria were inactive. Furthermore, nucleation sites reduced significantly and were derived from both the EPS of surviving microorganisms and un-hydrolyzed EPS from dead microorganisms. Consequently the microbial dolomites present nanometer-sized spherulitic and micron-sized irregular, spherical, and ovoidal morphologies. Overall, the microbial dolomites evolved from nanometer-sized granular (including spherulitic and pene-cubical granular) dolomites to (sub) micron-sized sheet-like, irregular, spherical and ovoidal dolomites, and then to macroscopic laminated, stromatolithic, uniform, and clotted dolostones. These findings reveal the correlation between morphological evolution of microbial dolomite and microbial activities showing the complexity and diversity of mineral (dolomite)-microbe interactions, and providing new insight into microbial biomineralization and microbial dolomite in the Precambrian era.     

Recent analog of gypsified microbial laminites and stromatolites in solar salt works and the Miocene gypsum deposits of Saudi Arabia and Egypt

Accumulation of microbial mats and stromatolites dominate in the crystallization ponds of solar salt works west of Alexandria, Egypt. These microbial mats are laminar in the permanent submerged part of the ponds. The microbial mats commonly form sites for growth of gypsum crystals during periods having higher salinity. In the dominant submerged part of the pond, domal stromatolites are common around groundwater seepage holes. In the shallow, intermittent margin of the ponds, the laminated microbial structure forms laterally close-linked hemispheroidal stromatolite type, with unidirectional and multidirectional ripple mark-like morphology on their surface. The microbial laminite and stromatolite types in the modern solar salt works are similar to the organic-rich Miocene gypsum beds of El-Barqan (west Alexandria, Egypt) and Rabigh (north Jeddah, Saudi Arabia). The Miocene organic-rich beds consist of interlayered dark-colored microbial laminae and light-colored gypsum laminae. These beds may have three different variations: regular even lamination, laterally closed-linked hemispheroidal stromatolites, and/or discrete hemispheroidal stromatolites. Petrographic examination of the microbial laminites and stromatolites in the solar salt works and the Miocene gypsum beds indicate that the dark-colored, organic-rich laminae are composed of micritized microbial laminae and/or brown organic filaments. In El-Barqan area, the light-colored gypsum-rich laminae are composed of either gypsum crystal fragments, or lenticular and prismatic gypsum. These gypsum crystals are either entrapped within the microbial filaments or are nucleated at the surface of the microbial laminae to form a radial pattern, whereas in Rabigh area, the light-colored gypsum-rich laminae are composed of secondary porphyrotopic, poikilotopic, or granular gypsum crystals. By comparison of the microbial structure in the Miocene gypsum beds with the recent occurrence of the microbial laminites and stromatolites in the solar salt works, it is demonstrated that the organic-rich Miocene gypsum beds were formed in a very shallow salina with slightly fluctuating brine levels.     

Microbe–mineral interactions: early carbonate precipitation in a hypersaline lake (Eleuthera Island, Bahamas)

Microbialites (benthic microbial carbonate deposits) were discovered in a hypersaline alkaline lake on Eleuthera Island (Bahamas). From the edge towards the centre of the lake, four main zones of precipitation could be distinguished: (1) millimetre‐sized clumps of Mg‐calcite on a thin microbial mat; (2) thicker and continuous carbonate crusts with columnar morphologies; (3) isolated patches of carbonate crust separated by a dark non‐calcified gelatinous mat; and (4) a dark microbial mat without precipitation. In thin section, the precipitate displayed a micropeloidal structure characterized by micritic micropeloids (strong autofluorescence) surrounded by microspar and spar cement (no fluorescence). Observations using scanning electron microscopy (SEM) equipped with a cryotransfer system indicate that micrite nucleation is initiated within a polymer biofilm that embeds microbial communities. These extracellular polymeric substances (EPS) are progressively replaced with high‐Mg calcite. Discontinuous EPS calcification generates a micropeloidal structure of the micrite, possibly resulting from the presence of clusters of coccoid or remnants of filamentous bacteria. At high magnification, the microstructure of the initial precipitate consists of 200–500 nm spheres. No precipitation is observed in or on the sheaths of cyanobacteria, and only a negligible amount of precipitation is directly associated with the well‐organized and active filamentous cyanobacteria (in deeper layers of the mat), indicating that carbonate precipitation is not associated with CO₂ uptake during photosynthesis. Instead, the precipitation occurs at the uppermost layer of the mat, which is composed of EPS, empty filamentous bacteria and coccoids (Gloeocapsa spp.). Two‐dimensional mapping of sulphate reduction shows high activity in close association with the carbonate precipitate at the top of the microbial mat. In combination, these findings suggest that net precipitation of calcium carbonate results from a temporal and spatial decoupling of the various microbial metabolic processes responsible for CaCO₃ precipitation and dissolution. Theoretically, partial degradation of EPS by aerobic heterotrophs or UV fuels sulphate‐reducing activity, which increases alkalinity in microdomains, inducing CaCO₃ precipitation. This degradation could also be responsible for EPS decarboxylation, which eliminates Ca²⁺‐binding capacity of the EPS and releases Ca²⁺ ions that were originally bound by carboxyl groups. At the end of these processes, the EPS biofilm is calcified and exhibits a micritic micropeloidal structure. The EPS‐free precipitate subsequently serves as a substrate for physico‐chemical precipitation of spar cement from the alkaline water of the lake. The micropeloidal structure has an intimate mixture of micrite and microspar comparable to microstructures of some fossil microbialites.     

Authigenic replacement of cyanobacterially precipitated calcium carbonate by aluminium‐silicates in giant microbialites of Lake Van (Turkey)

Studies of modern cyanobacterial mats and biofilms show that they can precipitate minerals as a consequence of metabolic and degradational activities paired with ambient hydrochemical conditions. This study looked at modern microbial mats forming giant, tower‐like, groundwater‐fed, calcareous microbialites in the world's largest, highly alkaline lake; Van Gölü (Lake Van), East Turkey. Results show that microbial systems play a role not only in carbonate precipitation but also in the formation of siliceous mineral phases. Transmitted light microscopy, scanning electron microscopy and spectral observations revealed that, within the extracellular polymeric substances excreted by the mats abundant minute aragonite grains precipitated first in vivo. These minute grains were quickly succeeded and/or supplemented in the dead biomass of the cyanobacterial mat by authigenic Al–Mg–Fe siliceous phases. Silicon dioxide is available in large concentrations in the highly alkaline water of Lake Van. Divalent cations (Ca and Mg) are delivered to the microbialites mostly by groundwater springs. The precipitation of the fine‐grained siliceous phases is probably mediated by bacteria degrading the cyanobacterial biomass and complexing the excessive cations with their extracellular polymeric envelopes. The bacteria serve as nucleation centres for the subsequent precipitation of siliceous mineral phases. Generally, the biphasic (calcareous and siliceous) mineralization – characterizing Lake Van microbialites – is controlled by their interior highly dynamic hydrogeochemical situation. There, the dramatically different alkaline lake water and the Ca–Mg‐charged groundwater mix at various rates. The early diagenetic replacement of the in vivo aragonite by authigenic siliceous phases significantly increases the fossilization potential of the mat‐forming cyanobacteria. Lake Van and its giant microbialite tufa towers act as a model explaining the transformation of early diagenetic mineral phases observed in many modern and ancient carbonate marine deposits, particularly those influenced by diffusion of silica‐enriched and metal‐enriched pore waters from below the water–sediment interface.     

Microbial Mats in Tibetan Hot Springs and their Contributions to the Cesium‐bearing Geyserite Ore Formation

Microbial mats, mainly dominated by filamentous algae Calothrix and Oscillatoria, are well developed in Tibetan hot springs. A great number of fossil microorganisms, which existed as algae lamination in thermal depositional cesium-bearing geyserite in this area, are identified as Calothrix and Oscillatoria through microexamination and culture experiments. These microbial mats show the ability to accumulate cesium from spring water to the extent of cesium concentration of 0.46–1.03% cell dry weight, 900 times higher than that in water, and capture large numbers of cesium-bearing opal grain. Silicon dioxide colloid in spring water replaces and fills with the organism and deposits on it to form algae laminated geyserite after dehydration and congelation. Cesium in the microbial mats and opal grain is then reserved in the geyserite. Eventually, cesium-bearing algae laminated geyserite is formed. Study on cesium distribution in geyserite also shows that cesium content in algae lamination, especially in heavily compacted algae lamination, is higher than in the opal layer. For geyserite with no algae lamination or other organism structure, which is generally formed in spring water with low silicon content, cesium accumulation and cesium-bearing opal grain assembled by the microbial mats are also indispensable. After the microbial mats accumulating cesium from spring water, silicon dioxide colloid poorly replaces and fills with the organism to form opal grain-bearing tremellose microbial mats. The shape and structure of the organisms are then destroyed, resulting in cesium-bearing geyserite with no algae lamination structure after dehydration and congelation. It is then concluded that microbial mats in the spring area contribute to the enrichment of cesium in the formation of cesium-bearing geyserite, and a biological genesis of the geyserite, besides of the physical and chemical genesis, is likely.     

基于微岩相分析的藻类在钙华沉积中的作用研究——以四川黄龙为例

在地表环境下,钙华沉积常常是物理化学和生物沉积过程共同作用的结果.藻类因其在钙华沉积环境中具有较大的生物量及其自身拥有多样的代谢方式,对钙华沉积过程和形态具有重要影响.本研究以四川黄龙钙华为例,通过对典型沉积点的水化学、藻类群落组成和现代钙华微岩相结构进行综合分析,来揭示藻类在钙华沉积中的作用.研究发现,黄龙钙华沉积环...     

Microbial dolomite in the sabkha environment of the middle Cambrian in the Tarim Basin,NW China

In the Tarim Basin, dolomite, which formed during the middle Cambrian associated with evaporites, has been attributed to the sabkha-style dolomite formed during the syndepositional period. The sedimentary microfacies suggests dolomite formation in the middle Cambrian is an ancient analogue of the sabkha of Abu Dhabi. Poorly crystallised dolomite spheroids or ovoids within or on the surface of dolomite crystals are a common phenomenon that can be widely observed in different stromatolites in the upper part of the intertidal zone and strongly resemble the morphology in modern sabkha dolomite-producing microbial mats and in microbial culture experiments. These lines of evidence suggest organic substrates for dolomite nucleation. Dolomite formation in the middle Cambrian in the Tarim Basin has been considered a classic analogue for carbonate and evaporate assemblages. The extent of microbial dolomite in ancient sabkha environments is proposed as an alternative model for dolomite formation, in which the mineral properties of organic substrates play a crucial role.     

Dolomite formation within microbial mats in the coastal sabkha of Abu Dhabi (United Arab Emirates)

Microbial mediation is the only demonstrated mechanism to precipitate dolomite under Earth surface conditions. A link between microbial activity and dolomite formation in the sabkha of Abu Dhabi has, until now, not been evaluated, even though this environment is cited frequently as the type analogue for many ancient evaporitic sequences. Such an evaluation is the purpose of this study, which is based on a geochemical and petrographic investigation of three sites located on the coastal sabkha of Abu Dhabi, along a transect from the intertidal to the supratidal zone. This investigation revealed a close association between microbial mats and dolomite, suggesting that microbes are involved in the mineralization process. Observations using scanning electron microscopy equipped with a cryotransfer system indicate that authigenic dolomite precipitates within the exopolymeric substances constituting the microbial mats. In current models, microbial dolomite precipitation is linked to an active microbial activity that sustains high pH and alkalinity and decreased sulphate concentrations in pore waters. Such models can be applied to the sabkha environment to explain dolomite formation within microbial mats present at the surface of the intertidal zone. By contrast, these models cannot be applied to the supratidal zone, where abundant dolomite is present within buried mats that no longer show signs of intensive microbial activity. As no abiotic mechanism is known to form dolomite at Earth surface conditions, two different hypotheses can reconcile this result. In a first scenario, all of the dolomite present in the supratidal zone formed in the past, when the mats were active at the surface. In a second scenario, dolomite formation continues within the buried and inactive mats. In order to explain dolomite formation in the absence of active microbial metabolisms, a revised microbial model is proposed in which the mineral‐template properties of exopolymeric substances play a crucial role.     

Carbonate precipitation in the alkaline lake Specchio di Venere (Pantelleria Island,Italy) and the possible role of microbial mats

Alkaline lakes like the hydrothermally affected lake Specchio di Venere (Pantelleria Island, Central Mediterranean) are typical geological settings harbouring calcified microbial mats. The present work is focused on the discrimination between biotic and abiotic processes driving carbonate precipitation in this lake, using hydrochemical, mineralogical and isotopic data. Hydrochemical analyses demonstrate that the lake is nearly 10−fold supersaturated with regard to aragonite and seasonally reaches hydromagnesite supersaturation. Microscopic observations depict organosedimentary laminated structures consisting of microbial communities and aragonitic precipitates, which are rather disseminated in pores than directly linked to microorganisms. Oxygen isotopic data indicate that authigenic carbonate crystallisation from evaporating water is the dominant precipitation process, further suggested by the absence of textural evidence of diagenetic processes. Conversely, the observed δ¹³C values reflect an influence of extracellular polymeric substances (EPS) on carbon fractionation during the precipitation process, due to the selective sequestration of ¹²C in the biomass. The above considerations suggest that at lake Specchio di Venere the carbonate precipitation is mainly of inorganic nature, but a minor role played by biologically influenced processes in microbial mats is not excluded.     

Microbial dolomite crusts from the carbonate platform off western India

Abstract The occurrence of Late Pleistocene dolomite crusts that occur at 64 m depth on the carbonate platform off western India is documented. Dolomite is the most predominant mineral in the crusts. In thin section, the crust consists of dolomitized microlaminae interspersed with detrital particles. Under scanning electron microscopy, these laminae are made up of tubular filaments or cellular structures of probable cyanobacterial origin. Dolomite crystals encrust or overgrow the surfaces of the microbial filaments and/or cells; progressive mineralization obliterates their morphology. Well-preserved microbial mats, sulphide minerals (pyrrhotite and marcasite) and the stable isotope composition of dolomite in the crusts indicate hypersaline and anoxic conditions during dolomite formation. The crusts are similar to dolomite stromatolites, and biogeochemical processes related to decaying microbial mats under anoxic conditions probably played an important role in dolomite precipitation. The dolomite is therefore primary and/or very early diagenetic in origin. The dolomite crusts are interpreted to be a composite of microbial dolomite overprinted by early burial organic dolomite. The results of this study suggest that a microbial model for dolomite formation may be relevant for the origin of ancient massive dolomites in marine successions characterized by cryptalgal laminites. The age of the crusts further suggests that the platform was situated at shallow subtidal depths during the Last Glacial Maximum.     

Formation of lacustrine dolomite in the late Miocene marginal lakes of the East Mediterranean (Northern Israel)

The study focuses on the formation of lacustrine dolomite in late Miocene lakes, located at the East Mediterranean margins (Northern Israel). These lakes deposited the sediments of the Bira (Tortonian) and Gesher (Messinian) formations that comprise sequences of dolostone and limestone. Dolostones are bedded, consist of small‐sized (<7 μm), Ca‐rich (52 to 56 mol %) crystals with relatively low ordering degrees, and present evidence for replacement of CaCO₃ components. Limestones are comprised of a wackestone to mudstone matrix, freshwater macrofossils and intraclasts (mainly in the Bira Formation). Sodium concentrations and isotope compositions differ between limestones and dolostones: Na = ~100 to 150 ppm; ~1000 to 2000 ppm; δ¹⁸O = ?3·8 to ?1·6‰; ?2·0 to +4·3‰; δ¹³C = ?9·0 to ?3·4‰; ?7·8 to 0‰ (VPDB), respectively. These results indicate a climate‐related sedimentation during the Tortonian and early Messinian. Wet conditions and positive freshwater inflow into the carbonate lake led to calcite precipitation due to intense phytoplankton blooms (limestone formation). Dry conditions and enhanced evaporation led to precipitation of evaporitic CaCO₃ in a terminal lake, which caused an increased Mg/Ca ratio in the residual waters and penecontemporaneous dolomitization (dolostone formation). The alternating lithofacies pattern reveals eleven short‐term wet–dry climate‐cycles during the Tortonian and early Messinian. A shift in the environmental conditions under which dolomite formed is indicated by a temporal decrease in δ¹⁸O of dolostones and Na content of dolomite crystals. These variations point to decreasing evaporation degrees and/or an increased mixing with meteoric waters towards the late Messinian. A temporal decrease in δ¹³C of dolostones and limestones and appearance of microbial structures in close association with dolomite suggest that microbial activity had an important role in allowing dolomite formation during the Messinian. Microbial mediation was apparently the main process that enabled local growth of dolomite under wet conditions during the latest Messinian.     

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.     

Nucleation and stabilization of Eocene dolomite in evaporative lacustrine deposits from central Tibetan plateau

In past decades, the formation of dolomite at low temperature has been widely studied in both natural systems and cultured experiments, yet the mechanism(s) involved in the nucleation and precipitation of dolomite remains unresolved. Late Eocene dolomitic deposits from core in the upper Niubao Formation (Lunpola Basin, central Tibetan Plateau, China) are selected as a case study to understand the dolomitization process(es) in the geological record. Dolomite formation in Lunpola Basin can be ascribed to a different mechanism forming the large quantities of replacive dolostones in the geological record; and provides a potential fossil analogue for primary dolomite precipitation at low temperature. This analogue consists of an alternation of laminated dolomitic beds, organic-rich and siliciclastic layers; formed in response to intense evaporation interpreted to take place in a continental shallow lake environment. Mineralogical, textural and stable isotopic evaluations suggest that the dolomite from those dense-clotted laminated beds is a primary precipitate. At the nanoscale, these dolomitic beds are composed of Ca–Mg carbonate globular nanocrystals (diameter 80 to 100 nm) embedded in an organic matrix and attached to clay flakes. Micro-infrared spectroscopy analyses have revealed the presence of aliphatic compounds in the organic matrix. Microscopic and elemental compositional studies suggest that clay surfaces may facilitate the nucleation of dolomite at low temperature in the same way as the organic matrix does. The dolomite laminae show values for δ¹⁸O_VPDB from −3.2 to −1.76‰ and for δ¹³C_VPDB from −2.62 to −3.78‰. Inferred δ¹⁸O_SMOW values of the lake water reveal typical evaporitic hydrological conditions. These findings provide a potential link to primary dolomite formation in ancient and modern sedimentary environments; and shed new light on the palaeoenvironmental conditions in central Tibet during the Eocene.     

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.     

Carbonate stromatolites from a Messinian hypersaline setting in the Caltanissetta Basin, Sicily: petrographic evidence of microbial activity and related stable isotope and rare earth element signatures

Lower Messinian stromatolites of the Calcare di Base Formation at Sutera in Sicily record periods of low sea‐level, strong evaporation and elevated salinity, thought to be associated with the onset of the Messinian Salinity Crisis. Overlying aragonitic limestones were precipitated in normal to slightly evaporative conditions, occasionally influenced by an influx of meteoric water. Evidence of bacterial involvement in carbonate formation is recorded in three dolomite‐rich stromatolite beds in the lower portion of the section that contain low domes with irregular crinkly millimetre‐scale lamination and small fenestrae. The dominant microfabrics are: (i) peloidal and clotted dolomicrite with calcite‐filled fenestrae; (ii) dolomicrite with bacterium‐like filaments and pores partially filled by calcite or black amorphous matter; and (iii) micrite in which fenestrae alternate with dark thin wispy micrite. The filaments resemble Beggiatoa‐like sulphur bacteria. Under scanning electron microscopy, the filaments consist of spherical aggregates of dolomite, interpreted to result from calcification of bacterial microcolonies. The dolomite crystals are commonly arranged as rounded grains that appear to be incorporated or absorbed into developing crystal faces. Biofilm‐like remains occur in voids between the filaments. The dolomite consistently shows negative δ¹³C values (down to ?11·3‰) and very positive δ¹⁸O (mean value 7·9‰) that suggest formation as primary precipitate with a substantial contribution of organic CO₂. Very negative δ¹³C values (down to ?31·6‰) of early diagenetic calcite associated with the dolomite suggest contribution of CO₂ originating by anaerobic methane oxidation. The shale‐normalized rare earth element patterns of Sutera stromatolites show features similar to those in present‐day microbial mats with enrichment in light rare earth elements, and M‐type tetrad effects (enrichment around Pr coupled to a decline around Nd and a peak around Sm and Eu). Taken together, the petrography and geochemistry of the Sutera stromatolites provide diverse and compelling evidence for microbial influence on carbonate precipitation.     

Carbonate and silicate biomineralization in a hypersaline microbial mat (Mesaieed sabkha,Qatar): Roles of bacteria,extracellular polymeric substances and viruses

In a modern peritidal microbial mat from Qatar, both biomediated carbonates and Mg‐rich clay minerals (palygorskite) were identified. The mat, ca 5 cm thick, shows a clear lamination reflecting different microbial communities. The initial precipitates within the top millimetres of the mat are composed of Ca–Mg–Si–Al–S amorphous nanoparticles (few tens of nanometres) that replace the ultrastructure of extracellular polymeric substances. The extracellular polymeric substances are enriched in the same cations and act as a substrate for mineral nucleation. Successively, crystallites of palygorskite fibres associated with carbonate nanocrystals develop, commonly surrounding bacterial bodies. Micron‐sized crystals of low‐Mg calcite are the most common precipitates, together with subordinate aragonite, very high‐Mg calcite/dolomite and ankerite. Pyrite nanocrystals and framboids are present in the deeper layers of the mat. Calcite crystallites form conical structures, circular to triangular/hexagonal in cross‐section, evolving to crystals with rhombohedral terminations; some crystallite bundles develop into dumb‐bell and stellate forms. Spheroidal organo‐mineral structures are also common within the mat. Nanospheres, a few tens of nanometres in diameter, occur attached to coccoid bacteria and within their cells; these are interpreted as permineralized viruses and could be significant as nuclei for crystallite‐crystal precipitation. Microspheres, 1 to 10 μm in diameter, result from intracellular permineralization within bacteria or the mineralization of the bacteria themselves. Carbonates and clay minerals are commonly aggregated to form peloids, tens of microns in size, surrounded by residual organic matter. Magnesium silicate and carbonate precipitation are likely to have been driven by pH – saturation index – redox changes within the mat, related to microenvironmental chemical changes induced by the microbes – extracellular polymeric substances – viruses and their degradation.     

Microbially mediated carbonates in the Holocene deposits from Sarliève, a small ancient lake of the French Massif Central, testify to the evolution of a restricted environment

Both the mineralogy and facies of lacustrine bio‐induced carbonates are controlled largely by hydrological factors that are highly dependent upon climatic influence. As such they are useful tools in characterizing ancient lake environments. In this way, the study of the sedimentary record from the small ancient Sarliève Lake (Limagne, Massif Central, France) aims to reconstruct the hydrological evolution during the Holocene, using petrographical, mineralogical and geochemical analyses. The fine‐grained marls, mainly calcitic, display numerous layers rich in pristine Ca‐dolomite, with small amounts of aragonite, which are clearly autochthonous. As these minerals are rather unusual in the temperate climatic context of western Europe, the question arises about their forming conditions, and therefore that of the lacustrine environment. Ca‐dolomite prevails at the base of the sequence as a massive dolomicrite layer and, in the middle part, it builds up most of the numerous laminae closely associated with organic matter. Scanning electron microscope observations reveal the abundance of tiny crystals (tens to hundreds of nanometres) mainly organized as microspheres looking like cocci or bacilli. Such a facies is interpreted as resulting from the fossilization of benthic microbial communities by dolomite precipitation following organic matter consumption and extracellular polymeric substance degradation. These microbial dolomites were precipitated in a saline environment, as a consequence of excess evaporation from the system, as is also suggested by their positive ?¹⁸O values. The facies sequence expresses the following evolution: (i) saline pan, i.e. endorheic stage with a perennial lowstand in lake level (Boreal to early Atlantic periods); (ii) large fluctuations in lake level with sporadic freshening of the system (Atlantic); (iii) open lake stage (sub‐boreal); and (iv) anthropogenic drainage (sub‐Atlantic).     

Biofilms, microbial mats and microbe-particle interactions: electron microscope observations from diatomaceous sediments

Sediments and diatoms from the mudflats of the Bay of Bourgneuf in western France were examined in an electron microscope study of biofilms and microbial mats. The sediments were kept in an aquarium for study and a diatom culture was made of the benthic diatoms. The sediment biofilm was composed of exopolymeric substances (EPS), incorporated clay particles and, rarely, bacteria. This film coated all particles at the sediment-water interface. Its surface morphology reflected its composition and internal structure. Thin films were smooth, whilst a lumpy structure or incorporated fibrils produced either a mammillated or ropy surface, and clays in the structure gave rise to a flaky morphology. At shallow depths in the sediment column (0.5 cm) the biofilm was already degraded. The biofilm coating degraded diatom frustules in the benthic diatom culture consisted of EPS and bacteria and presented a ragged appearance. Microbial mats occurred on the surface of the fresh littoral sediments as well as those in the aquarium, and on the wall of the aquarium. The mat on the surface of the aquarium sediments had an open structure with webs of fibrils and bacteria in the pore space. It formed in a relatively quiet environment. Pore space was more limited in the mat from the surface of the fresh littoral sediments, in which direct contact between biofilm coated particles was common. In the exposed environment of the aquarium wall there was a thick, resistant coating of EPS. In addition to binding particles together, the presence of mats and biofilms in sediments affects sediment physical properties such as porosity and permeability, the flux of dissolved substances in pore waters and the dissolution of particles and can, therefore, influence early diagenesis. Mats and biofilms seem to be more readily preserved in the geological record than the micro-organisms, such as bacteria, which produce them. Their identification in the sedimentary record would greatly aid interpretation of sediment genesis and evaluation of the microbial role in sediment formation.     

Chert spheroids of the Monterey Formation,California (USA): early‐diagenetic structures of bedded siliceous deposits

Chert spheroids are distinctive, early‐diagenetic features that occur in bedded siliceous deposits spanning the Phanerozoic. These features are distinct in structure and genesis from similar, concentrically banded ‘wood‐grain’ or ‘onion‐skin’ chert nodules from carbonate successions. In the Miocene Monterey Formation of California (USA), chert spheroids are irregular, concentrically banded nodules, which formed by a unique version of brittle differential compaction that results from the contrasting physical properties of chert and diatomite. During shortening, there is brittle fracture of diatomite around, and horizontally away from, the convex surface of strain‐resistant chert nodules. Unlike most older siliceous deposits, the Monterey Formation still preserves all stages of silica diagenesis, thus retaining textural, mineralogical and geochemical features key to unravelling the origin of chert spheroids and other enigmatic chert structures. Chert spheroids found in opal‐A diatomite form individual nodules composed of alternating bands of impure opal‐CT chert and pure opal‐CT or chalcedony. With increased burial diagenesis, surrounding diatomite transforms to bedded porcelanite or chert, and spheroids no longer form discrete nodules, yet still display characteristic concentric bands of pure and impure microcrystalline quartz and chalcedony. Petrographic observations show that the purer silica bands are composed of void‐filling cement that precipitated in curved dilational fractures, and do not reflect geochemical growth‐banding in the manner of Liesegang phenomena invoked to explain concentrically banded chert nodules in limestone. Chertification of bedded siliceous sediment can occur more shallowly (< 100 m) and rapidly (< 1 Myr) than the bulk silica phase transitions forming porcelanite or siliceous shale in the Monterey Formation and other hemipelagic/pelagic siliceous deposits. Early diagenesis is indicated by physical properties, deformational style and oxygen‐isotopic composition of chert spheroids. Early‐formed cherts formed by pore‐filling impregnation of the purest primary diatomaceous beds, along permeable fractures and in calcareous–siliceous strata.