sedimentary pyrite formation an update sedimentary pyrite formation during early diagenesis is a major process for controlling the oxygen level of the atmosphere and the sulfate concentration in seawater over geologic time the amount of pyrite that may form in a sediment is limited by the rates of supply of decomposable organic matter dissolved sulfate and reactive detrital iron minerals organic matter appears to be the major control on pyrite formation in normal non euxinic terrigenous marine sediments where dissolved sulfate and iron minerals are abundant by contrast pyrite formation in non marine freshwater sediments is severely limited by low concentrations of sulfate and this characteristic can be used to distinguish ancient organic rich fresh water shales from marine shales under marine euxinic conditions sufficient h2s is produced that the dominant control on pyrite formation is the availability of reactive iron minerals calculations based on a sulfur isotope model indicate that over phanerozoic time the worldwide average organic carbon to pyrite sulfur ratio of sedimentary rocks has varied considerably high cs ratios during permo carboniferous time can be explained by a shift of major organic deposition from the oceans to the land which resulted in the formation of vast coal swamps at that time low cs ratios compared to today during the early paleozoic can be explained in terms of a greater abundance of euxinic basins combined with deposition of a more reactive type of organic matter in the remaining oxygenated portions of the ocean the latter could have been due to lower oceanic oxygen levels and or a lack of transportation of refractory terrestrial organic matter to the marine environment due to the absence of vascular land plants at that time

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

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

dolomite formation and biogeochemical cycles in the phanerozoic summary based on present knowledge of the purely chemical controls on the kinetics of massive dolomite formation the abundance and distribution of dolomite throughout the phanerozoic remains an enigma sometimes referred to as the dolomite problem comparing dolomite abundance to secular variation in seawater chemistry indicates that some changes in seawater chemistry are more likely to have resulted from extensive dolomitization rather than to have caused it the recently formulated microbial dolomite model provides the opportunity to view the geological history of dolomite formation from a new perspective a biogeochemical approach to the dolomite problem reveals a plausible connection between phanerozoic geochemical cycles and dolomite formation in particular periods of more extensive dolomitization broadly correlate with diverse indicators of decreased oxygen levels in the atmosphere and oceans lowered oxygen levels would have fostered a more active community of anaerobic microbes including sulphate reducing bacteria which in turn could have led to more extensive dolomitization of marine carbonates

why are ancient rocky shores so uncommon the geologic history of rocky shore biotas has been neglected by paleontologists under present conditions of high continentality rocky shores account for more than 33 of the world s coastline they are generally located on shores facing narrow continental shelves where the pattern of global plate tectonics exerts much influence over their regional concentration the highest frequency of rocky shores occurs on islands associated with hot spots island arcs and convergent plate margins associated with subduction rocky shores situated in these settings are subject to recycling so their remains are rare in the stratigraphic record some passive continental margins including those along newly rifted oceans and those with low rates of sedimentation exhibit frequencies of rocky shores as high or higher than those found on many convergent plate margins these have a good chance of being retained in the stratigraphic record for geologically significant periods of time epicontinental flooding reduces the

surface complexation clues to dolomite growth calcium and magnesium adsorb in near stoichiometric proportions to dolomite over wide ranges in ca sup 2 mg sup 2 ionic strength and solution composition pointing to minimal mixing of metal cations between the caco sub 3 and mgco sub 3 layer edges exposed at the dolomite surface near neutral ph mg and ca adsorb as hydrated ions or in sulfate rich solutions as metal sulfate complexes near stoichiometric adsorption of ca and mg points to dehydration and subsequent carbonation of adsorbed mg as the likely rate limiting step for dolomite growth at near earth surface conditions we propose that one path for dolomite growth from low temperature natural waters is through the initial adsorption of mg sulfate complexes onto either 1 growing dolomite crystals or 2 rate limiting dolomite nucleii field relations as well as homogeneous synthesis at low temperatures 25 degrees c t 100 degrees c support this hypothesis and provide a mechanistic explanation for dolomite growth from sulfate rich natural waters 36 refs

dolomite abundance and stratigraphic age constraints on rates and mechanisms of phanerozoic dolostone formation increasing dolomite abundance with age relative to limestone has long been accepted as one of the general truisms of sedimentary geology a relationship which suggests that dolomitization is a cumulative process occurring slowly over the full burial history of a carbonate sequence however reevaluation of data in support of this assumption indicates that although relative dolomite abundances do change significantly throughout phanerozoic carbonate sequences no data set demonstrates any direct correlation between dolomite content and age whereas tabulation of available data does suggest greater amounts of dolomite formation during periods of continental flooding global mass balance calculations of potential magnesium sources also indicate that most dolomite has formed from marine or marine derived fluids at the earth9s surface this conclusion is indirectly supported by significant short term period scale changes in phanerozoic dolomite abundance a variation which would be more attenuated if dolomitization were dominantly a burial process dolomitization may be enhanced during times of global transgression higher atmospheric pco 2 and lower calcite saturation state in shallow marine settings

formation of dolomite at 40 80 c in the latemar carbonate buildup dolomites italy from clumped isotope thermometry the temperature of formation of replacement dolomite and 18 o h 2 o of dolomitizing fluid in the latemar carbonate buildup dolomites italy were estimated independently from carbonate clumped isotope thermometry dolomite formed at 42 72 9 11 c 2 standard deviations sd from fluid with 18 o h 2 o that averages 0 3 3 3 vienna standard mean ocean water 2 sd the estimated temperature and 18 o h 2 o are similar to those of modern diffuse flow fluids at mid ocean ridges the kind of fluid that has been proposed previously as the dolomitizing fluid in the latemar buildup based on the trace element compositions of dolomite calcite in limestone preserves original 18 o but records clumped isotope temperatures 44 76 9 11 c 2 sd that are higher than those at which the limestone formed temperature recorded by calcite but not 18 o was likely reset during dolomitization clumped isotope thermometry has great potential for application to studies of burial and diagenesis by retrieving independent estimates of temperature and 18 o h 2 o with uncertainties as low as 5 c 2 standard errors se and 0 75 2 se respectively from a single stable isotope analysis of a carbonate mineral

geochemistry of inorganic and organic sulphur in organic rich sediments from the peru margin abstract we have determined 1 the abundance and isotopic composition of pyrite monosulphide elemental sulphur organically bound sulphur and dissolved sulphide 2 the partition of ferric and ferrous iron 3 the organic carbon contents of sediments recovered at two sites drilled on the peru margin during leg 112 of the ocean drilling program sediments at both sites are characterised by high levels of organically bound sulphur obs obs comprises up to 50 of total sedimentary sulphur and up to 1 of bulk sediment the weight ratio of s to c in organic matter varies from 0 03 to 0 15 mean 0 10 such ratios are like those measured in lithologically similar but more deeply buried petroleum source rocks of the monterey and sisquoc formations in california the sulphur content of organic matter is not limited by the availability of porewater sulphide isotopic data suggest that sulphur is incorporated into organic matter within a metre of the sediment surface at least partly by reaction with polysulphides most inorganic sulphur occurs as pyrite pyrite formation occurred within surface sediments and was limited by the availability of reactive iron but despite highly reducing sulphidic conditions only 35 65 of the total iron was converted to sulphide 10 30 of the total iron still occurs as fe iii in surface sediments the isotopic composition of pyrite is similar to that of both iron monosulphide and dissolved sulphide either pyrite like monosulphide formed by direct reaction between dissolved sulphide and detrital iron and or the sulphur species responsible for converting fes to fes2 is isotopically similar to dissolved sulphide likely stoichiometries for the reaction between ferric iron and excess sulphide imply a maximum resulting fes2 fes ratio of 1 1 where pyrite dominates the pool of iron sulphides at least some pyrite must have formed by reaction between monosulphide and elemental sulphur and or polysulphide elemental sulphur s0 is most abundant in surface sediments and probably formed by oxidation of sulphide diffusing across the sediment water interface in surface sediments s0 is isotopically heavier than dissolved sulphide fes and fes2 and is unlikely to have been involved in the conversion of fes to fes2 polysulphides are thus implicated as the link between fes and fes2

early diagenetic processes fluxes and reaction rates in sediments of the south atlantic abstract porewaters recovered from sediment cores gravity corers box corers and multicorers from various subrogions of the south atlantic amazon river mouth equatorial upwelling congo river mouth benguela coastal upwelling area and angola basin were investigated geochemically objectives included determination of eh ph oxygen nitrate sulfate alkalinity phosphate ammonium fluoride sulfide cal mg sr fe mn and si in order to quantify organic matter diagenesis and related mineral precipitation and dissolution processes porewater profiles from the eastern upwelling areas of the south atlantic suggest that sulfate reduction in the deeper parts of the sediment may be attributed mainly to methane oxidation whereas organic matter degradation by sulfate reduction is restricted to the near surface sediments further a prominent concentration gradient change of sulfate and related mineralization products occurred typically in the upwelling sediments at a depth of 4 to 8 m far below the zone of bioturbation or bioirrigation because other sedimentological reasons seem to fail as explanations an early diagenetic sulfide oxidation to sulfate within the anoxic environment is discussed porewater profiles from the sediments of the amazon fan area are mainly influenced by reactions with fe iii phases the remarkable linearity of the concentration gradients of sulfate supports the idea of distinct reaction layers in these sediments in contrast to the upwelling sediments the sulfate gradient develops from the sediment surface to a sulfate reduction zone at a depth of 5 3 m probably because a reoxidation of sulfide is prevented by the reaction with iron oxides and the formation of iron sulfide minerals a comparison of organic matter degradation rates from the different areas of the south atlantic show the expected relationship to primary productivity oxygen is the dominating oxidant whereas organic matter degradation by nitrate mn iv and probably also fe iii reduction is several orders of magnitude lower sulfate reduction is quantitatively of similar importance as oxygen respiration in the organic rich sediments but may also include methane oxidation reoxidation of ammonium and mn2 by oxygen or nitrate do not alter significantly the estimation of organic matter degradation in the oxic zone but may contribute to the nitrate reduction in suboxic layers

influences of temperature and mg ca ratio on caco3 precipitates from seawater the mg ca ratio at which the calcium carbonate mineral that has pseudohomogeneously precipitated from seawater changes from calcite to aragonite was experimentally determined as a function of temperature results indicate a dramatic change in the critical mg ca ratio over a relatively small temperature range for example in normal seawater with a mg ca of 5 1 the critical temperature is 6 3 c at a temperature of 25 c however mg ca must be less than 1 4 0 1 for calcite to form these data indicate that paleoclimatic conditions at the time of carbonate deposition must be considered when attempting to make inferences about variation in other factors such as paleo p co 2 p pressure and paleo mg ca ratios that may control carbonate mineral formation by abiotic processes however the inverse relation between inferred global paleoclimatic conditions and the dominant type of caco 3 polymorph being abiotically deposited i e warm conditions and low mg calcite versus cool conditions and aragonite suggest that substantial changes must have taken place in ocean chemistry over phanerozoic time

anaerobic methane oxidation and the formation of dolomite abstract we examine the link between organic matter degradation anaerobic methane oxidation amo and sulfate depletion and explore how these processes potentially influence dolomitization we determined rates and depths of amo and dolomite formation for a variety of organic rich sites along the west african margin using data from ocean drilling program odp leg 175 rates of amo are calculated from the diffusive fluxes of ch4 and so4 and rates of dolomite formation are calculated from the diffusive flux of mg we find that the rates of dolomite formation are relatively constant regardless of the depth at which it is forming indicating that the diffusive fluxes of mg and ca are not limiting based upon the calculated log iap values log ksp values for dolomite were found to narrowly range between 16 1 and 16 4 dolomite formation is controlled in part by competition between amo and methanogenesis which controls the speciation of dissolved co2 amo increases the concentration of co32 through sulfate reduction favoring dolomite formation while methanogenesis increases the pco2 of the pore waters inhibiting dolomite formation by regulating the pco2 and alkalinity methanogenesis and amo can regulate the formation of dolomite in organic rich marine sediments in addition to providing a mechanistic link between amo and dolomite formation our findings provide a method by which the stability constant of dolomite can be calculated in modern sediments and allow prediction of regions and depth domains in which dolomite may be forming

deep sulfate reduction completely mediated by anaerobic methane oxidation in sediments of the upwelling area off namibia abstract porewater concentrations of sulfate methane and other relevant constituents were determined on four sediment cores from the high productivity upwelling area off namibia which were recovered from the continental slope at water depths of 1300 and 2000 m at all four stations a distinct sulfate methane transition zone was observed several meters below the seafloor in which both sulfate and methane are consumed nutrient porewater concentration profiles do not show gradient slope changes at the depths of the transition zones flux calculations carried out on the basis of the determined porewater profiles revealed that anaerobic methane oxidation accounts for 100 of deep sulfate reduction within the sulfate methane transition zone and consumes the total net diffusive sulfate flux a significant contribution of organic carbon oxidation to the reduction of sulfate at these depths could therefore be excluded we state that porewater profiles of sulfate with constant gradients above the transition zones are indicative for anaerobic methane oxidation controlling sulfate reduction

degree of supersaturation and precipitation of organogenic dolomite this paper integrates the degree of carbonate saturation into a general model for the origin of dolomite in organic rich marine sediments degradation of organic matter by sulfate reducing bacteria promotes early dolomite precipitation by simultaneously increasing the carbonate alkalinity and lowering the sulfate ion concentration to near zero the interstitial water in organic rich sediments of several deep sea drilling project sites where dolomite is believed to be precipitating is up to 10 sup 3 times supersaturated with respect to near ideal dolomite and up to 10 times supersaturated with respect to calcite the highly supersaturated interstitial waters appear to overcome low temperature kinetic barriers to precipitate a nonideal fine grained calcian dolomite the degree of supersaturation with respect to dolomite decreases and the interstitial water approaches carbonate equilibrium with increasing burial depth at several of these sites removal of sulfate ion is important because sulfate ion may inhibit dolomite precipitation a calcareous sediment is not required but the presence of calcite or aragonite appears to greatly enhance dolomitization by providing an additional source of ca and carbonate ions

oxygen isotope fractionation during synthesis of camg carbonate and implications for sedimentary dolomite formation hydrous camg carbonate was synthesized at temperatures of 40 degrees 60 degrees and 80 degrees c in the laboratory this material has very similar mineralogical characteristics to natural disordered dolomite from the coorong region in south australia besides the dolomite variable amounts of amorphous carbonate are present in all samples the oxygen isotope compositions of synthesized bulk carbonate samples e g amorphous carbonate plus dolomite plot significantly lower than the northrop and clayton 1966 dolomite water equilibrium fractionated degassing of the samples however revealed relatively low oxygen isotope values for fast reacting using 100 h3po4 amorphous carbonate in contrast slow reacting dolomite has more positive oxygen isotope values and calculated carbonate water oxygen isotope fractionation values are close to strongest known dolomite water oxygen isotope fractionation published earlier on variations of reaction stabilization temperatures during synthesis gave evidence for dolomite formation from hypersaline solutions by a dissolution reprecipitation process it is likely that amorphous carbonate has been a problem in defining the dolomite water fractionation in the past moreover dolomite associated amorphous carbonate contents probably led to incorrect speculations about lower oxygen isotope fractionation in a so called protodolomite water system copyright c 2005 elsevier ltd

bacterial fossils and microbial dolomite in triassic stromatolites triassic stromatolitic dolomite from italy preserves mineralized bacterial remains one of the first unequivocal identifications of such structures in the geological record they consist of empty spheroids 1 0 m diameter resembling coccoid bacteria and smaller 150 400 nm objects interpreted as dwarf bacterial forms occurring within and between syn sedimentary dolomite crystals moreover gently folded sheets 100 200 nm thick and several micrometers long form a sub polygonal network reminiscent of eps extracellular polymeric substance their granular textured surfaces suggest bacterial degradation of original organic matter these features confirm a biological origin for the stromatolites as in modern microbial mats and the preserved original geochemical signatures indicate early precipitation of mg carbonates induced through microbial sulfate reducing metabolic activities

primary fractionation and secondary alteration within an archean ultramafic lava flow fifteen samples across a 4 m thick komatiite flow from the val d or region in the southeast portion of the abitibi greenstone belt have been analysed for major oxides and trace elements including the rare earth elements ree the flow has been subjected to low grade regional metamorphism virtually all primary mineralogy olivine and clinopyroxene has been obliterated although primary textures are well preserved compositional differences between the upper spinifex textured portion and the underlying massive portion of the flow are largely consistent with the primary fractionation of approximately 30 olivine with a composition close to fo92

sulfate reduction and methane oxidation in continental margin sediments influenced by irrigation south east atlantic off namibia abstract sulfate reduction rates srr and concentrations of so 4 2 h 2 s pyrite sulfur total sulfur ch 4 and organic carbon were measured with high depth resolution through the entire length of the so 4 2 zone and well into the ch 4 zone at two continental slope stations in the eastern south atlantic benguela upwelling area the sediments were characterized by a high organic carbon content of approx 7 5 at geob 3703 and 3 7 at geob 3714 at geob 3703 so 4 2 concentrations decreased linearly with depth to about 40 m at the sulfate methane transition zone smt at 3 5 m while at geob 3714 so 4 2 remained at sea water concentration in the top 2 m of the sediment and then decreased linearly to about 70 m at the smt at 6 m direct rate measurements of srr 35 so 4 2 showed that the highest srr occurred within the surface 3 5 cm with peak rates of up to 20 and 7 nmol so 4 2 cm 3 day 1 at geob 3703 and geob 3714 respectively srr decreased quasi exponentially with depth at geob 3703 and the cumulative srr over the length of the so 4 2 zone resulted in an areal srr srr area of 1114 3493 mol m 2 day 1 median value 2221 mol m 2 day 1 at geob 3703 with more than 80 of the total sulfate reduction proceeding in the top 30 cm sediment at geob 3714 srr exhibited more scatter with a cumulative srr area of 398 1983 mol m 2 day 1 median value 1251 mol m 2 day 1 and with 60 of the total sulfate reduction occurring below a depth of 30 cm due partially to a deeply buried zone of sulfate reduction located between 3 and 5 m depths srr peaks were also observed in smt of both cores ostensibly associated with methane oxidation but with rates about 10 times lower than at the surface modeled srr balanced both methane oxidation rates and measured srr within the smt but severely underestimated by up to 89 the total srr area that were obtained from direct measurements modeled and measured srr were reconciled by including solute transport by irrigation described by a non local pore water exchange function which had values of up to 0 3 year 1 in the top sediment and decreased exponentially to zero i e no irrigation at 2 3 meters i e above smt these results suggested that co existing sulfate reduction processes and linear so 4 2 gradients can be maintained by a non local transport mechanism such as irrigation by which pore water in tubes or burrows is exchanged with bottom waters by activities of tube dwelling animals or some similar physical transport phenomenon i e bubble ebullition further support for an irrigation mechanism was found in the observations of open tubes of up to 8 mm id at depths down to 6 m which also contained fecal pellets indicating that these tubes were or had been inhabited

dissolved and particulate carbohydrates in contrasting marine sediments dissolved and particulate carbohydrates were examined in contrasting chesapeake bay estuarine and mid atlantic shelf slope break continental margin sediments particulate carbohydrates pchos rep resented 5 9 of the total sediment particulate organic carbon poc and pcho remineralization appeared to be a similar fraction of total sediment carbon oxidation or c ox when these results are compared with results from other coastal sediments and a pelagic turbidite pcho remineralization as a percentage of c ox did not vary by more than a factor of 2 3 over a 3 4 order of magnitude range in cox values the causes of this are not well understood but may be related to specific effects associated with the remineralization of highly altered organic matter mixtures under aerobic conditions dissolved carbohydrates dchos in these sediment pore waters ranged from 30 to 400 mm increased with depth in a manner similar to total doc and represented 10 to 55 of pore water doc in chesapeake bay sediments this percentage decreased with sediment depth while in these continental margin sediments it was constant upper 30 cm of the dchos in these pore waters 30 to 50 could be identified as individual aldoses monomeric neutral sugars and total aldose yields individual aldoses as a percentage of total doc were higher in these continental margin sediment pore waters 9 than they were in the estuarine sediment pore waters 5 a comparison of dcho and pcho concentrations in these sediments indicates that their concentrations are uncoupled and that pore water dcho concentrations are primarily controlled by sediment remineralization processes pore water dchos appeared to be preferentially found in the high molecular weight hmw doc pool and likely occur as some of the initial hmw intermediates produced and consumed during sediment poc remineralization these results also support past suggestions about the differing controls on carbon remineralization processes in continental margin versus estuarine sediments copyright 2000 elsevier science ltd

dissolved sulfide catalyzed precipitation of disordered dolomite implications for the formation mechanism of sedimentary dolomite abstract dolomite is a common mineral in the rock record however the rarity of modern dolomite and the notorious difficulty in synthesizing dolomite abiotically under normal earth surface conditions result in the long standing dolomite problem in sedimentary geology some modern dolomites are associated with sediments where microbial sulfate reduction is active however the role of sulfate reducing bacteria in dolomite formation is still under debate in this study we tested the effect of dissolved sulfide on the precipitation of ca mg carbonates which has been never explored before although dissolved sulfide is one of the major products of microbial sulfate reduction our results demonstrated that dissolved sulfide with a concentration of as low as several millimoles can enhance the mg2 incorporation into the calcitic structure and promote the crystallization of high magnesian calcite and disordered dolomite we also conducted seeded precipitation in experimental solutions containing dissolved sulfide which showed that calcite seeds can inhibit the precipitation of aragonite and monohydrocalcite caco3 h2o and induce more mg2 incorporation we propose that accumulated dissolved sulfide in pore waters in organic rich sediments may trigger the precipitation of disordered dolomite which can be considered as a precursor of some sedimentary dolomite our adsorption experiments revealed a strong adsorption of dissolved sulfide onto calcite faces we suggest that adsorbed dissolved sulfide can lower the energy barrier to the dehydration of mg2 water complexes on the growing carbonate surfaces this study sheds new light on understanding the role of sulfate reducing bacteria in dolomite formation and the formation mechanism of sedimentary dolomite

an organogenic origin for widespread dolomite in the cambrian eilean dubh formation northwestern scotland abstract dolomite precipitation from seawater is normally inhibited by the presence of sulfate the low activity of the carbonate ion and the high enthalpy of hydration of the magnesium ion however in modern microbial sediments anoxic degradation of cyanobacterial material by sulfate reducing bacteria can significantly alter ambient water chemistry sulfate is removed and enzymatic breakdown of proteins releases ammonia thereby increasing ph and carbonate alkalinity to levels necessary for dolomite formation magnesium may be supplied from complexed ion pairs in solution and from the breakdown of cyanobacterial sheaths and mucilage in the ancient past where benthic microbial communities dominated the depositional environment it is postulated that large scale shallow subsurface modif cation of ambient waters by sulfate reducing bacteria created conditions favorable to widespread dolomite formation early diagenetic cherts from the cambrian eilean dubh formation of northwestern scotland preserve successive stages of the taphonomic history of cyanobacterial biofabrics in sediments of a continuously aggrading shelf depth related sequential degradation of cyanobacterial mat is accompanied by the appearance and increase in abundance of authigenic dolomite culminating in a crystalline dolomitic fabric with only residual organic clots silicified oolitic grainstone fabrics preserve various ooid morphologies these form a diagenetically modified sequence in which progressive degradation of component microbial material together with leaching of the ooid shell is accompanied by the appearance and increase in abundance of intragranular authigenic dolomite total dissolution of ooids re ulted in the release of a package of crystals as sediment similar sequences are observed in peloids and intraclasts ensuing dolomitic rock fabrics bear no clue to their origin except where grains are preserved in early silicified windows these relationships can be explained by biochemical modification of porewaters during organic diagenesis and provide evidence for widespread authigenic dolomite formation in the shelf sediments this organic degradational model may serve as a basis for understanding the origin of thick platformal dolostone sequences of the proterozoic

diffusion and mass balance of mg during early dolomite formation monterey formation abstract diffusion from overlying seawater is capable of supplying enough mg to account for all of the early diagenetic dolomite observed in the monterey formation 0 5 20 vol the amount formed depends on the mg flux magnitude into the sediment which is proportional to the rate of dolomite precipitation and inversely proportional to the sediment accumulation rate the amount of dolomite formed is calculated for accumulation rates of 50 and 600 m ma using reaction rate constants obtained from the mg concentration profile of dsdp sites 479 533 and 147 and proposed profiles that assume significant dolomite formation in the uppermost tens of meters of sediment advective pore water flow from compaction decreases the mg flux and becomes increasingly significant as the accumulation rate increases and the reaction rate decreases advection alone during compaction supplies sufficient mg to account for a realistic maximum of 2 vol dolostone within a compacted section an approximate evaluation of the rayleigh number suggests that the low permeability of siliceous ooze prevents convective fluid flow at shallow burial depths the mg mass balance is calculated from dolomite abundance in monterey formation sections santa maria basin area california pore water and solid particle velocities are calculated as a function of sediment depth using a porosity depth relation for average siliceous sediment based on a composite of dsdp data the bulk sediment diffusion coefficient increases with sediment depth at a rate proportional to the geothermal gradient at shallow burial depths seawater is probably the only significant source of mg dolomite volcanic ash and clay minerals are the only significant sinks clay mineral organic matter and silica diagenesis may provide additional mg at deeper burial depths the more or less regular spacing of dolomitic layers may be controlled by the residence time of the dolomite forming layer within the uppermost sediment where the mg flux is a maximum

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

reactive iron in marine sediments abstract a combined field laboratory study has been undertaken to explore the mineralogy concentrations and reactivity towards sulfide of iron in marine sediments also considered is the importance of bacterial fe liberation in regulating pore water chemistry two contrasting marine environments are included one is the relatively fe poor foam site and the other is the fe rich sediment of the subaqueous mississippi delta results show that oxide minerals are the most important fe phases in early diagenetic pyrite formation however viewed separately lepidocrocite and ferrihydrite are more reactive towards sulfide than goethite and hematite when fe oxides are present in relatively high concentrations dissolved sulfide is nearly absent from sediment pore waters with concomitant high concentrations of dissolved fe even in the presence of active sulfide production by sulfate reduction a combination of experimental results and diagenetic modelling shows that in some sediments pore water fe finds it origin in the bacterial reduction of iron oxides this seems the case even though greater amounts of fe are reduced by reaction of sulfide with iron oxides it appears that distinct microenvironments may exist in marine sediments where in one microenvironment sulfide reacts with fe oxides locally precipitating fe sulfide minerals in another fe reduced and solubilized by microorganisms migrates freely into solution

holocene shallow subtidal dolomitization by near normal seawater northern belize calcic dolomite cements compose an average of 5 of the upper 4 3 m of subtidal deposits 18 o 2 compositions of the high sr dolomites mean october 1900 ppm together with near normal salinity and inherently normal mg ca ratio of pore fluids suggest precipitation from near normal seawater tidal and wind driven circulation of seawater through the sediments supplies most of the mg for dolomitization which appears to be promoted by elevated pore water alkalinity resulting from bacterially mediated oxidation of organic matter and locally early stages of methanogenesis rapid dolomitization here supports the idea that significant quantities of dolomite can form syndepositionally from normal seawater in shallow subtidal deposits