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

dolomitized cells within chert of the permian assistencia formation parana basin brazil abstract dolomitic microscopic structures in the form of microspheres horseshoe shaped objects and thin botryoidal crusts found within microfossiliferous chert within stromatolites of the evaporite bed eb of the permian assistencia formation irati subgroup parana basin brazil have been investigated by means of optical microscopy x ray fluorescence scanning electron microscopy raman spectrometry and energy dispersive x ray spectrometry the microspheres were identified as dolomitized coccoidal cyanobacteria based on similarity in size spheroidal and paired hemispheroidal morphologies and colonial habit to co occurring silicified organic walled cyanobacteria embedded within the same microfabric and rock samples the co occurrence of dolomite pyrite framboids and abundant dispersed carbonaceous material and silicified cells is consistent with a hypersaline depositional environment with abundant cyanobacterial mats and elevated mg2 ca2 ratios and reducing conditions with active anoxic microbial processes near the water bio sediment interface the abundance of extracellular polymeric substances facilitated anoxic microbial processes sulfate reduction providing essential conditions for possible primary microbially induced dolomitization in most of the dolomitized cells dolomite occurs only as an external layer in fully dolomitized cells magnesium is richest in the outermost layer presumably the dolomitization process was favored by the presence of anoxic microbial degraders and negatively charged functional groups at the surface of the cyanobacterial cells botryoidal dolomite rims of silica filled fenestrae formed by a similar process and inherited the botryoidal morphology of the cell as originally lining the fenestrae silicification interrupted the dolomitization of the largely organic biosediment mostly by permineralization but locally by substitution thereby preserving not only dolomitic microspheres but also huge numbers of structurally well preserved organic walled cyanobacteria and portions of microbial mat clearly dolomitization began very early in the microbial mats prior to compaction of the sediment or full obliteration of cellular remains followed very closely by silicification thereby impeding continued degradation and providing a window onto very well preserved permian microbial mats

microbial mats as bioreactors populations processes and products microbial mats are dynamic and complex ecosystems exhibiting spatial and temporal heterogeneity the physical chemical environment is typified by steep gradients and distinct microenvironments these microenvironments support a great diversity of species with a wide range of metabolic processes these processes often result in coupled reactions and biogeochemical cycles and produce important end products such as trace gases and mineral precipitates the latter can impact the composition and character of the sediment imparting a biosignature these biosignatures can be preserved in the rock record and are useful in the interpretation of fossil record on earth and possibly as an indication of life on other planetary bodies the modern marine stromatolites of the exuma cays bahamas provide an ideal system for studying the populations processes and products in a microbial ecosystem using a multidisciplinary approach in order to acquire redox energy microbial populations need to carry out metabolic reactions at rates faster than the equivalent chemical abiotic reactions as such microbes can be viewed as bioreactors that preferably oxidize carbon to co2 to maximize the energy yield the study of the microbial role in carbonate sedimentation and lithification in these stromatolites provides a picture of microbial mats as bioreactors producing a biosignature

the role of sulphate reducing bacteria and cyanobacteria in dolomite formation in distal ephemeral lakes of the coorong region south australia abstract the dolomitic distal ephemeral lakes of the coorong region of south australia are dynamic systems in which the concentrations of solutes generally increase during late spring and summer when the rate of evaporation greatly exceeds aqueous input during late evaporation active bacterial sulphate reduction occurs in uppermost anoxic lake sediments as rising salinity and then h2s toxicity kills off the macrobiota these hypersaline lakewaters are characterised by high ph and elevated concentrations of carbonate and sulphate ions magnesium concentrated in cyanobacterial cells and sheaths is released into the strongly electrolytic alkaline lake brines from lake margin stromatolites and mats during desiccation and may explain the remarkable increase in mg levels recorded at this time continued evaporation of the lakewaters produces a halite crust overlying the dolomite sulphate free residual puddles and the absence of gypsum indicates that all sulphate is removed by sulphate reducing bacteria dolomite forms in situ as a primary precipitate from these microbially mediated lake porewaters and both the morphology and size distribution of dolomite grains is identical to bacterial cells it is not proven exactly when dolomite precipitation occurs but the submicron sized grains and multiple defects in a disordered lattice indicate that precipitation is rapid and follows bacterial removal of sulphate which is known to inhibit dolomite formation bacterial sulphate reduction and cyanobacterial degradation may thus lead to the removal of all kinetic inhibitors to dolomite formation and provide a mechanism for dolomite precipitation around bacterial cells in shallow subsurface sediments during the late stages of evaporation in adjacent non dolomitic lakes sulphate is present throughout evaporation so that other minerals principally aragonite and hydromagnesite are precipitated

sedimentary pyrite a window into the microbial past early diagenetic pyrite forms as a result of microbial processes in sediments but has received little attention as a potential source of microbial fossils sedimentary pyrite grains archean to jurassic in age were examined by scanning and transmission electron microscopy tem ion milling was essential for the preparation of electron transparent tem samples most pyrite grains revealed coccoid rod shaped and even filamentous features that are interpreted as microbial identification of microbial remains in sedimentary pyrite may greatly expand our knowledge of microbial life in the sedimentary record combined with geochemical characterization the study of pyritized microbes in the geologic record may in the future enable us to interpret changes in geochemical signatures more realistically in terms of different sulfate reducing communities sedimentary pyrite grains may also represent a good prospect to further our knowledge of past life on mars

microbial dolomite crusts from the carbonate platform off western india 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

a stable isotope study of microbial dolomite formation in the coorong region south australia abstract the coorong region of south australia is a classic location for the study of modern dolomite formation a number of ephemeral lakes here contain dolomite whilst other lakes in close proximity contain aragonite with minor magnesite our previous field and experimental work has revealed that sulphate reducing bacteria play a key role in overcoming kinetic inhibitors to dolomite formation in this area we here use a combination of oxygen carbon and sulphur isotopes to help to further constrain the processes leading to dolomite precipitation in modern hypersaline environments we report isotopic data from four dolomite and three aragonite containing lakes 34 s data for dissolved lake and porewater sulphates reveal 34 s enrichment of residual sulphate in all seven lakes consistent with bulk closed system microbial fractionation by sulphate reducing bacteria calculations using temperature dependent oxygen isotope fractionation factors between dolomite and the solution from which it precipitated are consistent with a strong microbial component to carbonate precipitation in these lakes a comparison of 18 o data from dolomite and aragonite sediment and from their associated lakewaters indicates seasonal mineral precipitation occurs late in the evaporative cycle of the lakes within a yoghurt like saturated mud horizon coincident with the zone of sulphate reduction surprisingly 13 c data from the carbonates do not show the characteristic wide range of values often associated with organogenic carbonates but instead show that these bacterially mediated precipitates incorporate carbon primarily from the inorganic lakewater reservoir partially diluted by an organic component a coorong type microbial model of dolomite formation may be particularly applicable to for example precambrian sedimentary dolomites where benthic microbial communities which are today restricted to extreme environments dominated the shallow marine ecosystem prior to the emergence of metazoa

presence of sulfate does not inhibit low temperature dolomite precipitation abstract the hypothesis that sulfate inhibits dolomite formation evolved from geochemical studies of porewaters from deep sea sedimentary sequences and has been tested with hydrothermal experiments we examined the sulfate inhibition factor using aerobic culture experiments with virgibacillus marismortui and halomonas meridiana two moderately halophilic aerobic bacteria which metabolize independent of sulfate concentration the culture experiments were conducted at 25 and 35 c using variable so42 concentrations 0 14 28 and 56 mm and demonstrate that halophilic aerobic bacteria mediate direct precipitation of dolomite with or without so42 in the culture media which simulate dolomite occurrences commonly found under the earth s surface conditions hence we report that the presence of sulfate does not inhibit dolomite precipitation further we hypothesize that if sedimentary dolomite is a direct precipitate as in our low temperature culture experiments the kinetic factors involved are likely to be quite different from those governing a dolomite replacement reaction such as in hydrothermal experiments consequently the occurrence and presumably growth of dolomite in so42 rich aerobic cultures may shed new light on the long standing dolomite problem

cyanobacterial precipitation of gypsum calcite and magnesite from natural alkaline lake water results from transmission electron microscopy provide direct evidence for cyanobacterial biomineralization of gypsum and calcite in aquatic environments laboratory simulations using filter sterilized natural lake water inoculated with synechococcus sp isolated from fayette ville green lake new york revealed epicellular biomineralization of gypsum calcite and magnesite experimental electron microscopical and sedimentological evidence indicates that synechococcus is responsible for a major proportion of the marl sediment and carbonate bioherms in green lake the elucidated role of synechococcus in biomineralization and its ubiquitous distribution in nature have widespread implications for cyanobacterial mineralization in marine and freshwater environments since late archean time

microbial primary dolomite from a norian carbonate platform northern calabria southern italy the origin of fine grained dolomite in peritidal rocks has been the subject of much debate recently and evidence is presented here for a microbial origin of this dolomite type in the norian dolomia principale of northern calabria southern italy microbial carbonates there consist of stromatolites thrombolites and aphanitic dolomites high relief thrombolites and stromatolites characterize sub tidal facies and low relief and planar stromatolites with local oncoids typify the inter supratidal facies skeletal remains are very rare in the latter whereas a relatively rich biota of skeletal cyanophycea red algae and foraminifera is present in the sub tidal facies some 75 of the succession consists of fabric preserving dolomite especially within the microbial facies whereas the rest is composed of coarse dolomite with little fabric preservation three end members of dolomite replacement fabric are distinguished type 1 and type 2 fabric retentive with crystal size 5 and 5 60 m respectively and type 3 fabric destructive with larger crystals from 60 to several hundred microns in addition there are dolomite cements precipitated in the central parts of primary cavities during later diagenesis microbialite textures in stromatolites are generally composed of thin dark micritic laminae of type 1 dolomite alternating with thicker lighter coloured laminae of the coarser type 2 dolomite thrombolites are composed of dark micritic clotted fabrics with peloids composed of type 1 dolomite surrounded by coarser type 2 dolomite marine fibrous cement crusts are also present now composed of type 2 dolomite scanning electron microscope observations of the organic rich micritic laminae and clots of the inter supratidal microbialites reveal the presence of spherical structures which are interpreted as mineralized bacterial remains these probably derived from the fossilization of micron sized coccoid bacteria and spheroidal ovoidal nanometre scale dwarf type bacterial forms furthermore there are traces of degraded organic matter probably also of bacterial origin the microbial dolomites were precipitated in a hypersaline environment most likely through evaporative dolomitization as suggested by the excess ca in the dolomites the small crystal size and the positive 18o values the occurrence of fossilized bacteria and organic matter in the fabric preserving dolomite of the microbialites could indicate an involvement of bacteria and organic matter degradation in the precipitation of syn sedimentary dolomite

microbially mediated carbonate precipitation in a hypersaline lake big pond eleuthera bahamas microbial metabolism impacts the degree of carbonate saturation by changing the total alkalinity and calcium availability this can result in the precipitation of carbonate minerals and thus the formation of microbialites here the microbial metabolic activity the characteristics and turnover of the extracellular polymeric substances and the physicochemical conditions in the water column and sediments of a hypersaline lake big pond bahamas were determined to identify the driving forces in microbialite formation a conceptual model for organomineralization within the active part of the microbial mats that cover the lake sediments is presented geochemical modelling indicated an oversaturation with respect to carbonates including calcite aragonite and dolomite but these minerals were never observed to precipitate at the mat water interface this failure is attributed to the capacity of the water column and upper layers of the microbial mat to bind calcium a layer of high mg calcite was present 4 to 6 mm below the surface of the mat just beneath the horizons of maximum photosynthesis and aerobic respiration this carbonate layer was associated with the zone of maximum sulphate reduction it is postulated that extracellular polymeric substances and low molecular weight organic carbon produced at the surface i e the cyanobacterial layer of the mat bind calcium both aerobic and anaerobic heterotrophic microbes consume extracellular polymeric substances each process accounting for approximately half of the total consumption and low molecular weight organic carbon liberating calcium and producing inorganic carbon the combination of these geochemical changes can increase the carbonate saturation index which may result in carbonate precipitation in conclusion the formation and degradation of extracellular polymeric substances as well as sulphate reduction may play a pivotal role in the formation of microbialites both in marine and hypersaline environments

microbially mediated dolomite in cambrian stromatolites from the tarim basin north west china implications for the role of organic substrate on dolomite precipitation abstract 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 delta o 18 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

bacterial origin of east australian continental margin phosphorites many models of the origin of marine phosphorites require a sediment rich in organic matter which by decomposition releases phosphorus for the precipitation of carbonate fluorapatite1 7 this concept is useful in explaining contemporary phosphorite in areas of very high productivity off the coasts of peru chile and south west africa8 10 where there are high organic matter fluxes to the sea floor4 7 11 it does not explain the origin of marine phosphorite deposits which formed in regions of limited oceanic upwelling and productivity12 14 the east australian continental margin an area of phosphogenesis throughout the late pleistocene and holocene13 14 is a modern analogue of an east coast phosphogenic province15 17 with low productivity over the upper slope region where the most recent phosphorites have been found18 evidence is reported here for the carbonate fluorapatite in the east australian phosphorites being located within bacterial cellular structures and a model proposed for the origin of these deposits through the slow bacterial assimilation of phosphorus from seawater in an area of restricted sedimentation

overlapping of pedogenesis and meteoric diagenesis in distal alluvial and shallow lacustrine deposits in the madrid miocene basin spain the miocene distal alluvial fan and palustrine deposits of the madrid basin paracuellos de jarama area were examined to establish the sequence of its pedogenic diagenetic processes and the main factors controlling them in this area the diagenetic processes operated not only on carbonates as commonly studied but also in high magnesium clays and opaline cherts this paper provides a dynamic model for saline alkaline lake margins that complements the existing freshwater palustrine model three sections ber pel and upc containing limestones sepiolite dolostones and opaline cherts were examined these represent the entire transition from alluvial fan deposit to lake environment the alluvial fan deposits pel section show the most complex sequence of processes after a weak edaphic imprint the primary mudstone and siltstones are affected by silicification opaline levels formed mainly by selective replacement of sepiolites and later dolomitization several types of dolomite are present rounded crystals spherules and globular bodies being the most characteristic in the ponds situated at the foot of the alluvial fans or in interfan areas sepiolite precipitated within free water bodies ber section and an intense pedogenesis led to the formation of palustrine sepiolite deposits later the intense silicification of the sepiolite produced lenticular opaline levels that were locally transformed to quartz by aging in the shallow lakes upc section palustrine limestones and sepiolite were deposited the carbonates are partially affected by silicification the sepiolite becoming completely silicified the opaline levels clearly preserve the structure of the limestones and sepiolite host rocks all the opaline levels show local aging processes the silicification processes were different in the three settings due to the interplay of groundwater with sedimentary environments and facies in the distal alluvial fan sediments of the pel section the initial host rock affected by silicification is not preserved due to the later dolomitization that erased both it and its textures the silicification environment was therefore not easy to determine in the ber and upc section the main silicification took place in groundwater influenced environments but evidence was seen of cements and silicifications in vadose environments in all study settings the overlapping of pedogenic vadose and groundwater processes was controlled by changes in the position of the water table four stages were concluded to explain the transformation from the primary deposits to the later dolomitization process and the formation of vadose cements the majority of the silicifications seen occurred as responses to changes in the water table position linked to the aggradation of this closed basin in all the studied environments the sepiolite deposits were preferentially silicified their fibrous structure and high absorption capacity helping to retain interstitial fluids moreover sepiolite and opal are stable under relatively similar geochemical conditions in arid environments the dissolution of the sepiolite caused an increase in silica in the interstitial fluids favouring silicification and ruling out the need of a biogenic source the replacement of limestones by silica is usually driven by variations in ph and salinity which are very common in surface environments such as shallow lakes and soils

microbial precipitation of dolomite in methanogenic groundwater we report low temperature microbial precipitation of dolomite in dilute natural waters from both field and laboratory experiments in a freshwater aquifer microorganisms colonize basalt and nucleate nonstoichiometric dolomite on cell walls in the laboratory ordered dolomite formed at near equilibrium conditions from groundwater with molar mg ca ratios of 1 dolomite was absent in sterile experiments geochemical and microbiological data suggest that methanogens are the dominant metabolic guild in this system and are integral to dolomite precipitation we hypothesize that the attached microbial consortium reacts with the basalt surface releasing mg and ca into solution which drives dolomite precipitation via nucleation on the cell wall these findings provide insight into the long standing dolomite problem and suggest a fundamental role for microbial processes in the formation of dolomite across a wide range of environmental conditions

geochemical evidence for lacustrine microbial blooms in the vast permian main karoo parana falkland islands and huab basins of southwestern gondwana early permian black pyritic shale units i e the whitehill irati and huab formations and black rock member in southwestern gondwana basins have elevated 13c values of total organic carbon up to 17 pdb hydrogen indices between 300 and 1000 mg co2 g c and oxygen indices 30 mg co2 g c these data suggest a manifestation of a microbial bloom event values for 13c between 26 and 22 pdb hydrogen 100 mg co2 g c and oxygen indices of total organic carbon above and below these rock units are typical for palaeozoic terrestrial type iii organic matter carbon 13 isotope stratigraphy concur with palaeontological evidence that these formations are stratigraphical equivalents and therefore that the microbial blooms covered a vast area 5 million km2 possibly earth s most expansive microbial bloom the palaeoenvironment of the rock units preceding and including the black shales was most likely lacustrine with fresh to brackish water as shown by stable isotope c o and s evidence from organic matter carbonates and pyrite the implication is that a broad tectonic belt which formed as a result of compressional tectonics during the late carboniferous to early permian from the palaeo west must have been sufficiently well developed to cut off any contact with seawater earlier than predicted late permian from previous stratigraphic and sedimentological studies stable isotope data supported by mineralogical evidence indicate that conditions particularly in the upper portions of the lacustrine oil shales were brackish and locally may have been evaporitic we envisage that the microbial blooms possibly botryococcus peaked in the upper half of the black shale units conditions rapidly became unfavourable for microbial blooms across the entire basin in the overlying formations manifested by a change from oil shales type i organic matter to organic poor type iii shales this may possibly have been a consequence of tectonic activity and interrelated causes stable isotope data of carbonates in the overlying sediments indicate that in the palaeo north the basin became evaporitic drying up and in the palaeo southern part of the basin high latitude altitude water flooded the basin and so brought to a close the microbial blooms

christmas island lagoonal lakes models for the deposition of carbonate evaporite organic laminated sediments the atoll of christmas island now known as kiritimati in the kiribati republic central pacific lies at about 28n in the intertropical convergence zone much of the surface area of the atoll ca 360 km 2 is occupied by numerous lakes in which carbonate evaporite calcium sulfate halite and organic layers are deposited observations suggest that deposition of these different laminae is controlled by climatic and biologic factors it is thought that periodic climatic variations such as el nino southern oscillations enso events which bring heavy rainfall to the atoll result in the succession of the precipitation of carbonate minerals during periods after dilution of hypersaline waters by heavy rains followed by evaporitic minerals carbonate calcium sulfate halite when salinity increases through evaporation thick up to 5 cm microbial essentially cyanobacterial mats develop continuously on the lake bottom surfaces providing the sediment with an important total organic carbon 2 5 organic contribution in the form of an internal geometrically structured network in which the authigenic minerals precipitate the high bioproductivity of these microbial populations is reflected in low d 13 c values of sedimentary organic carbon 214 to 217 interpreted as being the result of high atmospheric co2 demand geochim cosmochim acta 56 1992 335 the well laminated organic layers present in the sediment profile result from the death and burial of microbial populations at the time of severe climatic events storms heavy rainfall these lagoonal lakes provide a model for the deposition of carbonate and organic matter in an evaporitic environment the high ratio of deposited carbonate vs sulfate 1 chloride when compared to low ratio in evaporitic salinas results from both a lack of limitation of calcium magnesium and carbonate ions in a carbonate reef environment and active processes of high mg calcite precipitation organomineralization q 2001 elsevier science b v all rights reserved

occurrence of phreatic dolocrete within tertiary clastic deposits of kuwait arabian gulf abstract the term dolocrete is used in the present study to describe siliciclastic sediments which are partially or completely cemented and or replaced by terrestrial phreatic dolomite several successive dolocrete profiles occur within the subsurface tertiary fluviatile muddy sand and mudstone deposits in kuwait city three zones were recognized within these dolocrete profiles these are in descending order 1 dolocrete band 2 dolocrete nodules and 3 incipient dolocrete dolocrete also occurs within the compact green mudstone layers the studied dolocrete comprises detrital grains inherited from the host sediment and authigenic minerals precipitated during the dolocretization processes the detrital grains include mainly quartz feldspars illite and smectite the abundance of authigenic minerals dolomite calcite and palygorskite relative to detrital grains reflects the degree of dolocrete maturation mature dolocrete is chiefly composed of dolomite and palygorskite several dolomite fabrics and textures were recognized however dolocretic dolomite is generally present as incomplete rhombohedra with spiky terminations variation in the nature of host sediment and diagenetic conditions are responsible for the degree of dolocretization and diversity of fabrics and textures it is suggested that the dolocrete was developed by the precipitation of dolomite from pore solution saturated with respect to dolomite within the phreatic zone three main sources of chemicals required for dolocretization are suggested 1 mg rich groundwater from the dolomitic dammam formation 2 mg and co 2 released from clay minerals and organic matter in the host sediment mud matrix and 3 infiltrated meteoric water

spheroidal dolomites in a visean karst system bacterial induced origin spheroidal dolomite crystals occur in the karstified top of a dinantian dolomite sequence in eastern belgium the spheroidal dolomite crystals are best developed at the base of the karst system the dolomite crystals are characterized by a spherulitic or dumb bell inclusion pattern and are overgrown by dolomite cements with a rhombohedral outline they are considered to be bacterially related precipitates based on 1 textural similarities with documented bacteriogenic precipitates 2 the presence of bacterial microspheres and framboidal pyrite embedded within the dolomite and 3 their general geological setting the geochemical characteristics of the dolomites and associated minerals support a bacterial origin the ubiquity of framboidal pyrite depleted in 34s 34s 22 4 to 25 5 ocdt testifies to a period of bacterial sulphate reduction the isotopic composition of the spheroidal dolomites 13c 2 4 to 3 2 opdb and 18o 3 8 to 3 4 opdb suggest a contribution from oxidized organic carbon produced during bacterial sulphate reduction sulphate reduction may also result in a concomitant 18o depletion if the system is nearly closed it is however evident from the sulphur isotopic composition of associated framboidal pyrite that the system was fairly open the 18o depletion of the spheroidal dolomite crystals 18o 3 8 to 3 4 opdb and their occurrence adjacent to and within karst cavities suggests a mixing zone origin with a significant proportion of freshwater in it the rhombohedral cement overgrowths have calculated 18o values in the range of 0 to 5 3 opdb which reflect precipitation from normal to slightly evaporated contemporaneous seawater

microbes produce nanobacteria like structures avoiding cell entombment microsedimentary structures referred to as nanobacteria like particles were described from modern carbonate environments where they form in close spatial association with sulfate reducing bacteria srb however the exact mechanism of their formation as well as their paleontological significance remains controversial here we report on an investigation of microbe mineral interactions in experimentally produced carbonate globules the experiments were carried out under anoxic conditions at 30 c with desulfovibrio brasiliensis a srb known to mediate dolomite formation we observed that extracellular polymeric substances eps secreted by the microbial community play a key role in the mineralization process nanobacteria like particles represent the early stage of carbonate nucleation within the eps which progressively evolve to larger globules displaying a grainy texture we excluded the possibilities that these structures are fossils of nanobacteria dissolution surfaces or artifacts created during sample preparation d brasiliensis cells are predominantly located outside of the eps aggregates where mineral growth takes place as a result they remain mobile and are rarely entombed within the mineral this self preservation behavior may not be limited to d brasiliensis other microbes may produce or may have produced during the geological past biogenic minerals through a similar process mineralization within eps explains why microbial relics are not necessarily present in biogenic carbonates

bacterially induced dolomite precipitation in anoxic culture experiments to study the process of microbial mediated dolomite formation growth experiments were carried out with selected bacterial cultures under anoxic environmental conditions simulating those found in lagoa vermelha a hypersaline lagoon in brazil where dolomite precipitation occurs specifically we report the isolation of a particular strain of sulfate reducing bacteria lvform6 from lagoa vermelha sediment which apparently promotes the formation of nonstoichiometric dolomite sulfate reducing bacteria grown in a synthetic liquid medium produced dolomite during 30 days incubation at 30 c the precipitates have morphologies similar to those observed in lagoa vermelha sediment our results demonstrate that sulfate reducing bacteria can influence dolomite precipitation under controlled lowtemperature anoxic conditions and imply that anaerobic microorganisms can play an important role in carbonate sedimentation they may have been particularly significant in earth s earliest history when a more reducing atmosphere existed

iron framboids in the hydrocarbon related middle devonian hollard mound of the anti atlas mountain range in morocco evidence of potential microbial biosignatures iron framboids in the context of a middle devonian hydrocarbon seep conical mound anti atlas morocco have been thoroughly investigated through a combination of techniques including optical and high resolution scanning electron microscopy x ray diffraction energy dispersive x ray spectroscopy raman microscopy and time of flight secondary ion mass spectroscopy framboids occur embedded in laminated carbonates of the mound and are precipitated along the veins that crosscut it and served as the conduits for channeled reduced hydrocarbon rich fluids the morphology structure and composition of the framboids contribute to the reconstruction of the complex interplay between the advected fluids and the associated biological and or abiological processes a comparison of our dataset with that from modern framboids formed under similar conditions indicates that the fe rich framboids represent replaced primary pyrite framboids produced as a consequence of bacterial sulfate reduction and the anaerobic oxidation of methane

microbial nucleation of calcium carbonate in the precambrian microbial sulfate reduction is thought to stimulate carbonate precipitation in modern stromatolites yet whether this metabolism was important in shaping precambrian stromatolites is unknown here we use geochemical modeling to suggest that the influence of sulfate reduction on the saturation index of calcite si is negligible when seawater is in equilibrium with high pco 2 as is thought for the precambrian our laboratory experiments with heterotrophic bacteria in a medium mimicking precambrian seawater chemistry show that even if sulfate reduction does not significantly change the si the presence of bacteria stimulates calcite precipitation over sterile controls by effectively increasing the si over a ph range from 7 3 to 7 8 under our experimental conditions dead cells stimulate in situ carbonate precipitation equally if not more than active sulfate reducing bacteria heterogeneous nucleation of calcite by microbial cell material appears to be the driving mechanism that explains this phenomenon

calcification of cyanobacterial mats in solar lake sinai pore water samples were obtained from the shallow water part of solar lake sinai where luxurious cyanobacterial mats grow these samples were analyzed for ca sup 2 mg sup 2 sr sup 2 cl sup so sub 4 sup 2 and titration alkalinity ta to determine the role of cyanobacterial growth and degradation on the calcification of the mats the data are modeled thermodynamically to predict mineral pore water equilibria the data support earlier bacterial and sedimentological studies suggesting that the degradation of the cyanobacterial mat via sulfate reduction is of major importance in the calcification process 34 references 1 figure 2 tables

mesoproterozoic carbon dioxide levels inferred from calcified cyanobacteria filamentous and shrub like carbonate fabrics produced by in vivo cyanobacterial sheath calcification in stromatolites of the ca 1200 ma society cliffs formation baffin and bylot islands arctic canada are 400 m y older than previously reported examples in vivo sheath calcification is promoted by carbon dioxide concentrating mechanisms ccms and is a direct ecophysiological link to atmospheric co 2 concentration ccms are induced in present day cyanobacteria under experimental conditions when pco 2 is below 0 36 10 times present atmospheric level pal society cliffs calcified cyanobacteria consequently imply pco 2 levels of 2 of 7 10 pal in the late mesoproterozoic combined petro graphic experimental and modeling results therefore suggest that mesoproterozoic pco 2 concentrations were not substantially different from phanerozoic values and were significantly less than previous estimates of up to 200 pal assuming 10 lower solar luminosity in the late mesoproterozoic pco 2 levels of 10 pal or less require the presence of additional greenhouse gases for maintenance of an ice free earth at 10 pal pco 2 methane concentrations of 100 200 ppm would have been sufficient to sustain warm earth surface conditions the low atmospheric oxygen and limited marine sulfate concentrations required to sustain atmospheric methane provide additional support for sulfur isotope models that suggest protracted oxygenation of earth9s proterozoic biosphere

dolomite occurrence evolution and economically important associations abstract dolomite is not a simple mineral it can form as a primary precipitate a diagenetic replacement or as a hydrothermal metamorphic phase all that it requires is permeability a mechanism that facilitates fluid flow and a sufficient supply of magnesium dolomite can form in lakes on or beneath the shallow seafloor in zones of brine reflux and in early to late burial settings it may form from seawater from continental waters from the mixing of basinal brines the mixing of hypersaline brine with seawater or the mixing of seawater with meteoric water or via the cooling of basinal brines bacterial metabolism may aid the process of precipitation in settings where sulfate reducing species flourish and microbial action may control primary precipitation in some hypersaline anoxic lake settings dolomite is a metastable mineral early formed crystals can be replaced by later more stable phases with such replacements repeated a number of times during burial and metamorphism each new phase is formed by the partial or complete dissolution of an earlier dolomite this continual re equilibration during burial detracts from the ability of trace elements to indicate depositional conditions and resets the oxygen isotope signature of the dolomite at progressively higher temperatures because subsurface dolomite evolves via dissolution and reprecipitation a bed of dolomite can retain or create porosity and permeability to much greater burial depths and into higher temperature realms than a limestone counterpart dolomitization also creates new crystals with new rhomb growth following the dissolution of less stable precursors repetition of this process without complete pore cementation can generate intercrystalline porosity a number of times in the rock s burial history intercrystalline porosity is a highly interconnected style of porosity that gives dolomite reservoirs their good fluid storage capacity and efficient drainage the fact that many dolomite reservoirs formed via brine reflux means that they sit beneath an evaporite seal in both platform and basinwide evaporite settings the same association of evaporites sulfate source and entrained hydrocarbons means that burial conditions are also suitable for thermochemical sulfate reduction and the precipitation of base metals this tends to occur at higher temperatures 60 c 80 c and so the resulting dolomites tend to be ferroan and consist of saddle shaped crystals

fluid inclusion analysis of twinned selenite gypsum beds from the miocene of the madrid basin spain implication on dolomite bioformation this research work is centred on continental lacustrine gypsum deposits of miocene age cropping out in the easternmost part of the madrid basin these gypsum deposits accumulated in a continental saline lake are characterized by a spectacular distinctive christmas tree morphology and a peculiar dolomite replacement a combination of microscopic petrography and scanning electron microscopy and analytical techniques fluid inclusion microthermometry x ray energy dispersive spectroscopy and x ray diffractometry was used in order to study the crystallographic distribution and the composition of the fluid inclusions within the gypsum the objectives were to characterize the continental brine from which the mineral precipitated and to detect mineral and element traces that could indicate early diagenetic processes altering the gypsum deposits data from primary fluid inclusions indicated that gypsum precipitated from an aqueous fluid lake water of low to moderate total salinity between 20 and 90 g l nacl secondary fluid inclusions represent interstitial lake brine in contact with gypsum slightly enriched in total salt content as crystal formation proceeded textural ultrastructural and microanalytical analysis indicate that the presence of dolomite precipitates inside the gypsum layers is related to the microbial colonization of the gypsum deposits and the biomineralization of the cell walls and extracellular polymeric substances around the cells our investigation emphasizes necessity of a multidisciplinary approach to assess geobiological processes

miocene phosphorites from the murray ridge northwestern arabian sea abstract phosphorites from the murray ridge nw arabian sea comprise nodules bioclasts and bone fragments the nodules are made up of a homogeneous light colored phosphate nucleus consisting of rivulariacean filamentous cyanobacteria and a thin dark grey colored phosphate cortex showing abundant microbial filaments and microborings the bioclasts comprise of 14 14 5 ma old planktonic foraminifers accepted as the time of deposition spherical to ovoid shaped apatite microparticles resembling fossil bacteria are distinct components in the bioclasts bone fragments exhibit apatite fillings the nodules and bone fragments consist entirely of carbonate fluorapatite cfa with low al k and th concentrations suggesting absence of continental detritus shale normalized ree patterns of the samples support a seawater derived composition the highly uniform initial nd values of 4 8 to 5 1 are interpreted as the seawater value at the onset of phosphatization 14 ma ago in contrast 87sr 86sr ratios show a large range of 0 709055 to 0 709124 corresponding to unusually young stratigraphic ages of 1 to 3 ma the data are interpreted as evidence for post depositional sr exchange of the recrystallizing phosphorites with fluids isotopically not much different from modern seawater it is concluded that the phosphorites formed under oxic shallow water conditions where microbial populations assimilated phosphorus primarily from seawater and mediated precipitation of cfa during early diagenesis at the sediment water interface on different substrates

nucleation of calcium carbonate on bacterial nanoglobules nucleation of calcium carbonate on microbial cell material may have been the dominant mode of microbial carbonate formation during most of earth s history current knowledge predicts that nucleation takes place on the cell surface or on extracellular polymeric substances however the initial nucleation steps have not been described in detail and the process remains elusive here we describe the bacterial nucleation of calcium carbonate at the nanometer scale in our precipitation experiment with sulfate reducing bacteria srb the bulk of calcium carbonate precipitates on hundreds of individual globules 60 200 nm in diameter globules originate from the srb cell surface but calcify significantly only when released to the culture medium similar globules have been observed albeit at a much larger scale in other bacterial precipitation experiments and in many natural microbial carbonates suggesting that the process we describe could be an important step in microbial calcification

modern non marine dolomite in evaporitic playas of western victoria australia abstract although considerable effort has been made during the past 30 years to understand the occurrence of recent dolomite there are surprisingly few well documented examples of dolomite precipitation in modern continental lacustrine environments fine grained poorly ordered non stoichiometric dolomite occurs in association with magnesite and clay minerals in the modern and holocene sediment of numerous evaporitic lacustrine settings in western victoria we conclude that this dolomite is primary i e nucleated from solution and accumulated as a primary sediment rather than secondary replacement of a precursor carbonate cores from selected basins show that this dolomite micrite has been accumulating for over 10 000 years

microbially influenced formation of mg calcite and ca dolomite in the presence of exopolymeric substances produced by sulphate reducing bacteria some species of sulphate reducing bacteria srb are known to mediate the formation of dolomite and mg calcite however their exact role in the mineralization process remains elusive here we present the result of a laboratory experiment that was designed to test whether formation of carbonate minerals by srb can occur in the absence of living cells through passive mineralization of their exopolymeric substances eps srb capable of mediating dolomite were cultivated in the laboratory allowing them to secrete eps microbial activity within the cultures was subsequently inhibited with antibiotics only after this step ca2 and mg2 were added to the solution and carbonate minerals could form mg calcite and disordered ca dolomite precipitated in association with eps the mol of mg2 in the crystals increased with longer incubation times this result demonstrates that organic compounds produced by srb can mediate the formation of ca mg carbonates in the absence of an active metabolism

on the possibility of a ridge current along the hawaiian islands four evenly spaced aircraft deployed expendable bathythermograph and concurrent satellite advanced very high resolution radiometer avhrr surveys were made over an extended area during a 1 year period to observe possible ridge currents along the hawaiian islands predicted or hypothesized by other investigators none of the surveys found extended currents running along the ridge instead fields of energetic eddies were found and a curious cusp shaped sea surface temperature pattern was observed in two of the avhrr fields apparent cyclonic currents around the island of hawaii were also observed we conclude that either ridge currents do not exist or that they exist but are intermittent episodic in nature or exist in a form more complicated than could be observed by this study

kuwaiti dolocrete petrology geochemistry and groundwater origin abstract near surface sediments in southern kuwait show extensive development of duricrusts the host materials are siliciclastic sandstones of the post eocene kuwait group inland the duricrusts are dominantly pedogenic calcrete with some silcrete and gypcrete whereas within 10 20 km of the coast dolomite is the dominant duricrust mineral both these dolocretes and the inland calcretes display a similar maturation sequence in which carbonate rich nodules develop and coalesce carbonate progressively replacing and displacing detrital grains the dolomite of the dolocretes forms mosaics of crystals typically 10 70 m in size varying from simple rhombs to spherulites an intermediate morphology named artichoke dolomite from its appearance in sem is particularly abundant authigenic palygorskite is associated with the dolomite dissolution of cores or zones within dolomite crystals has occurred calcite is present as sparry crystals always post dating dolomite and is the expected precipitate from present day soil and groundwaters chemical analyses of dolomite show highly negative values of 13 c to 10 7 pdb and 18 o varying from 0 6 to 3 3 pdb the oxygen isotope values are interpreted as reflecting evaporation of a marine based fluid manganese values of around 1000 ppm show that this fluid was reducing strontium data show variability reflecting mineral fluid reactions the general absence of metastable carbonates and presence of zoning in dolomite crystals suggests that meteoric dilution of seawater also occurred given that the duricrusts lack biogenic features the light carbon isotope values are taken to indicate oxidation of seeping hydrocarbons the dolocretes are interpreted as groundwater precipitates near the water table of a brackish water body formed at a time of higher relative sea level than today

modern and late holocene dolomite formation manito lake saskatchewan canada abstract major advances have occurred in our understanding of modern dolomite formation and penecontemporaneous dolomitization over the past several decades manito lake located in west central saskatchewan canada is a large 65 km 2 deep z max 22 m perennial saline 45 ppt tds lake in which modern and late holocene dolomite coexists with other endogenic and authigenic carbonate precipitates including aragonite monohydrocalcite calcite and mg calcite like many other lacustrine dolomites manito lake dolomite is microcrystalline less than 1 m to 5 m ca rich and poor to moderately ordered it occurs as relatively pure hardgrounds and as a component of nearshore microbialites it also forms isopachous cements in consolidated siliciclastic shoreline sediments manito lake dolomite is most likely forming by mainly biomediated precipitation at or near the sediment water interface i in pore spaces of coarse siliciclastic sediments i e beachrock ii as fine laminae associated with microbialites and iii as a major component of mudstone hardgrounds and pavements

ca carbonates precipitation and limestone genesis the microbiogeologist point of view abstract experiments show that the production of carbonate particles by heterotrophic bacteria follows different ways in heterotrophy the passive carbonatogenesis is generated by modifications of the medium that lead to the accumulation of carbonate and bicarbonate ions and to the precipitation of solid particles it is induced by several metabolic pathways of the nitrogen cycle ammonification of amino acids degradation of urea and uric acid dissimilatory reduction of nitrates and of the sulphur cycle dissimilatory reduction of sulphates the active carbonatogenesis is independent of the mentioned metabolic pathways the carbonate particles are produced by ionic exchanges through the cell membrane following still poorly known mechanisms in autotrophy non methylotrophic methanogenesis and cyanobacterial photosynthesis also may contribute to the precipitation of carbonates autotrophic carbonates as carbonatogenesis is neither restricted to particular taxonomic groups of bacteria nor to specific environments it has been an ubiquitous phenomenon since precambrian times carbonatogenesis is the response of heterotrophic bacterial communities to an enrichment of the milieu in organic matter after a phase of latency there is an exponential increase of bacterial numbers together with the accumulation of metabolic end products these induce a ph increase and an accumulation of carbonate and hydrogenocarbonate ions in the medium this phase ends into a steady state when most part of the initial enrichment is consumed and there is a balance between death and growth in bacterial populations particulate carbonatogenesis occurs during the exponential phase and ends more or less after the beginning of the steady state the active carbonatogenesis seems to start first and to be followed by the passive one which induces the growth of initially produced particles in eutrophic conditions the first solid products are patches that appear on the surface of the bacterial bodies and coalesce until forming a rigid coating and or particles excreted from the cell all these tiny particles assemble into biomineral aggregates which often display precrystalline structures these aggregates grow and form biocrystalline build ups which progressively display more crystalline structures with growth in oligotrophic conditions the primary solid products are rapidly smoothed in the crystalline structure and leave no trace in present aqueous environments apart from deep ocean the potential efficiency of heterotrophic bacterial carbonatogenesis in ca carbonate sedimentation is much higher than autotrophic or abiotic processes it much more likely accounts for extensive apparently abiotic limestone formation than any of the latter as far as biodetrital particles are concerned it may be observed that the shells and tests of organisms are built from the activity of cellular organites which are nowadays considered by a number of biologists as endosymbiotic bacteria thus apart from probably mythical purely evaporitic and autotrophic ones most limestones must be considered as principally of heterotrophic bacterial origin as the carbon of limestones is issued from organic matter bacterial heterotrophic carbonatogenesis appears as a fundamental phenomenon in the relationships between atmosphere and lithosphere during the biogeological evolution of the earth

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

spheroidal dolomites origin by hydrocarbon seepage spheroidal dolomite cements are a pervasive and distinctive feature in five exposed lithologies of different geological age in kuwait the spheroids range in diameter from 5 350 m have concentric zones and nuclei of fluid inclusions with or without a radial fabric and compositions varying from near stoichiometric to ca56 mg44 all spheroids appear to be primary in origin with no evidence of replacement some concentric zones show selective calcitization and or leaching most of these features are confined to within 30 m of the surface consequently spheroidal dolomites recognizable at depth in ancient sequences may be indicative of a local unconformity the dolomite distributions are areally correlative with known areas of hydrocarbon seepage the latter being confined to prominent oil field anticlinal trends it is proposed that the dolomitization was caused by groundwaters carrying hydrocarbons to the surface which were then oxidized to carbon dioxide the gas bubbles may have acted as nuclei for spheroid growth with a possible inducement by bacteria which have an affinity for hydrocarbons the implication is that the regional distribution of spheroidal dolomites may be an indicator of a potential reservoir facies at depth

groundwater dolocretes from the upper triassic of the paris basin france a case study of an arid continental diagenetic facies thick dolomite cemented horizons dolocretes occur within a fluvial sandstone mudstone sequence of late triassic age in the western part of the paris basin france two types of dolomites can be distinguished a nodular dolomitic beds less than a few metres thick which formed within mottled overbank siltstones and mudstones and b massive dolomite up to 16 m thick which occurs in coarse grained channel sandstones and conglomerates the majority of the dolomite consists of a finely crystalline groundmass of dolomicrospar and less commonly dolomicrite glaebules irregular spar filled cracks spheroidal dolomite silicification and vuggy porosity are locally abundant in the massive dolomite in contrast biologically induced micromorphological features such as rhizocretions and alveolar septal fabrics were observed in the thin nodular dolomite beds the dolomite is near stoichiometric well ordered and non ferroan 18o values range from 7 7 to 0 4 o pdb and 18o values range from 5 1 to 1 8 0 pdb and no obvious difference in the stable isotopic composition between both types of dolomites was observed sr isotope ratios range from 0 7101 to 0 7126 and are invariably higher than the contemporary triassic sea water a vadose pedogenic origin for the thin dolocrete layers is indicated by the occurrence of rhizocretions and other biological structures several features however argue against a pedogenic origin for the massive carbonates most notably the absence of biologically induced structures the occurrence in coarse grained channel and not overbank deposits and the great thickness these units are thus interpreted as groundwater in origin phreatic calcretes of quaternary age widespread in inland australia are regarded as a modern analogue for the triassic paris basin dolocretes petrographic observations argue in favour of primary proto dolomite precipitation although early diagenetic replacement of calcite by proto dolomite cannot be ruled out strontium and carbon isotope data of early diagenetic dolocrete cements and oxygen isotope data of early diagenetic silica indicate an entirely non marine continental origin for the groundwaters the poorly ordered and non stoichiometric protodolomite probably underwent stabilization upon further burial resulting in a near stoichiometric well ordered dolomite that clearly lacks evidence for pervasive recrystallization

shrimp u pb zircon dating and palynology of bentonitic layers from the permian irati formation parana basin brazil abstract this paper presents the first shrimp zircon age data from bentonitic ash fall layers intercalated with the irati sedimentary rocks as well as palynofossils retrieved from the petrobras six mine parana state southern brazil the permian irati formation is one the most important oil source horizons within the parana basin and consists mainly of siltstones gray claystones as well as organic rich claystones intercalated with limestones zircon morphology based on cathodoluminescence images includes two different populations a dominant population of euhedral prismatic elongate to acicular grains which are most likely related to an ash fall volcanism and a population of rounded to large prismatic grains that were interpreted as detrital grains shrimp analysis performed on the euhedral and prismatic grains revealed an age of ca 278 4 2 2 ma 7 points with 95 confidence interpreted as the crystallization age of the volcanic eruption based on this new dating the irati formation should be placed on the lower permian cisuralian artinskian in age modifying substantially the traditional ages previously attributed to this unit the palynofossils from this level include key species of the lueckisporites virkkiae zone such as l virkkiae l densicorpus l stenotaeniatus weylandites lucifer alisporites splendens typical species of this zone also occur in african and other south american argentina permian strata allowing stratigraphical correlations the origin of the ash falls is not clearly defined it may be related either to calc alkaline arc magmatism associated to the sanrafaelica orogeny 275 and 250 ma or to bimodal volcanic events associated to an early intracontinental rift developed within southwestern gondwana at ca 278 my the dating of this unit is significative to calibrate biostratigraphic schemes along the parana basin as well as equivalent zones in gondwana areas mainly in its occidental portion