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1.
In the present study, a mixed-flow steady-state bio-reactor was designed to biomineralize CO2 as a consequence of photosynthesis from active Synechococcus sp. Dissolved CO2, generated by constant air bubbling of inorganic and cyanobacteria stock solutions, was the only source of inorganic carbon. The release of hydroxide ion by cyanobacteria from photosynthesis maintained highly alkaline pH conditions. In the presence of Ca2+ and carbonate species, this led to calcite supersaturation under steady state conditions. Ca2+ remained constant throughout the experiments showing the presence of steady state conditions. Similarly, the Synechococcus sp. biomass concentration remained stable within uncertainty. A gradual pH decrease was observed for the highest Ca2+ condition coinciding with the formation of CaCO3. The high degree of supersaturation, under steady-state conditions, contributed to the stabilization of calcite and maintained a constant driving force for the mineral nucleation and growth. For the highest Ca2+ condition a fast crystal growth rate was consistent with rapid calcite precipitation as suggested further by affinity calculations. Although saturation state based kinetic precipitation models cannot accurately reflect the controls on crystal growth kinetics or reliably predict growth mechanisms, the relatively reaction orders obtained from modeling of calcite precipitation rates as function of decreasing carbonate concentration suggest that the precipitation occurred via surface-controlled rate determining reactions. These high reaction orders support in addition the hypothesis that crystal growth proceeded through complex surface controlled mechanisms. In conclusion, the steady state supersaturated conditions generated by a constant cyanobacteria biomass and metabolic activity strongly suggest that these microorganisms could be used for the development of efficient CO2 sequestration methods in a controlled large-scale environment.  相似文献   

2.
The tufa record and hydrochemical characteristics of the River Piedra in the Monasterio de Piedra Natural Park (NE Spain) were studied for 6 years. The mean discharge of this river was 1.22 m3/s. The water was supersaturated with calcium carbonate. The HCO3 −, Ca2+ and TDIC concentrations decreased along the 0.5-km-long studied stretch, whereas the calcite SI showed no systematic downstream or seasonal variation over the same stretch. Several sedimentary subenvironments exist in which four broad types of tufa facies form: (1) Dense laminated tufa (stromatolites), (2) Dense to porous, massive tufa, (3) Porous, coarsely laminated tufa with bryophytes and algae, and (4) Dense, hard, laminated deposits in caves. The half-yearly period thickness and weight of sediment accumulated on 14 tablets installed in several subenvironments showed that the deposition rate was greater in fast flowing river areas and in stepped waterfalls, and lower in slow flowing or standing river areas and in spray and splash areas. Mechanical CO2 outgassing is the main factor controlling calcite precipitation on the river bed and in waterfalls, but this process does not explain the seasonal changes in depositional rates. The deposition rates showed a half-yearly period pattern recorded in all fluvial subenvironments persistent over time (5.26 mm, 0.86 g/cm2 in warm periods; 2.26 mm, 0.13 g/cm2 in cool periods). Mass balance calculations showed higher calcite mass values in warm (21.58 mg/L) than in cool (13.68 mg/L) periods. This biannual variation is mainly attributed to the seasonal differences in temperature that caused changes in inorganic calcite precipitation rate and in biomass and the correlative photosynthetic activity. Tufa sedimentation was therefore controlled by both physicochemical and biological processes. The results of this study may help test depositional rates and their environmental controls and thus assess the climatic and hydrological significance of ancient tufas in semi-arid conditions, in particular in the Quaternary.  相似文献   

3.
Dendritic calcite forms in an active cold-water tufa system in association with extracellular polymeric substances (EPS) that discontinuously coat bryophytes and cyanobacteria. Dendrites consist of 100–200 nm thick calcite fibres that form 3D lattice-like domains. In each dendrite domain, fibres have three structurally equal orientations, which correspond in disposition to radii from the centre of a calcite unit cell to the convex triple face junctions on its surface. Fibres do not form in the orientation of the c-axis. The external form of each dendrite has the shape of half of a shortened octahedron, with an upper triangular surface parallel to the substrate. Dendrite nucleation takes place on or in microbial EPS, whether microbial cells are present or not, and is probably effected by attraction of Ca2+ cations to negatively charged EPS, together with CO2-degassing and concomitant pH increase of supersaturated spring water in stream splash zones. Ensuing dendrite growth is abiogenic and controlled by diffusion. Dendrite c-axes are perpendicular to the substrate, probably because the negative charge of EPS forces the orientation of Ca2+ and CO planes within the developing dendrite crystal to be parallel to the EPS film surface. Dendrites are eventually filled and overgrown by solid, syntaxial calcite, which gradually and completely obliterates the dendrites as more familiar calcite crystal forms develop. No trace of the dendritic nucleus remains in the rock record. Calcite crystal nucleation may take place by this mechanism in many marine and meteoric settings, given that microbial EPS is now assumed to be virtually ubiquitous in these environments. This phenomenon could contribute to the development of familiar fabrics such as marine micrite cement and fibrous calcite cement, radial ooids, peloids, ‘abiogenic’ stromatolites, sea floor precipitates, microbialites, tufa, travertine, speleothems, and some meteoric cements. It may also contribute to the substrate-normal orientation of c-axes of common cement fabrics.  相似文献   

4.
Hourly resolved cave air PCO2 and cave drip water hydrochemical data illustrate that calcite deposition on stalagmites can be modulated by prior calcite precipitation (PCP) on extremely short timescales. A very clear second-order covariation between cave air PCO2 and drip water Ca2+ concentrations during the winter months demonstrates the effects of degassing-induced PCP on drip water chemistry. Estimating the strength of the cave air PCO2 control on PCP is possible because the PCP signal is so clear; at our drip site a one ppm shift in Ca2+ concentrations requires a PCO2 shift of between 333 and 667 ppm. This value will undoubtedly vary from site to site, depending on drip water flow rate, residence time, drip water-cave air PCO2 differential, and availability of low PCO2 void spaces in the vadose zone above the cave. High-resolution cave environmental measurements were used to model calcite deposition on one stalagmite in Crag Cave, SW Ireland, and modelled growth over the study period (222 μm over 171 days) is extremely similar to the amount of actual calcite growth (240 μm) over the same time interval, strongly suggesting that equations used to estimate stalagmite growth rates are valid. Although cave air PCO2 appears to control drip water hydrochemistry in the winter, drip water dilution caused by rain events may have played a larger role during the summer, as evidenced by a series of sudden drops in Ca2+ concentrations (dilution) followed by much more gradual increases in drip water Ca2+ concentrations (slow addition of diffuse water). This research demonstrates that PCP on stalactites, cave ceilings, and void spaces within the karst above the cave partially controls drip water chemistry, and that thorough characterisation of this process at individual caves is necessary to most accurately interpret climate records from those sites.  相似文献   

5.
Many Recent and fossil freshwater tufa stromatolites contain millimetre‐scale, alternating laminae of dense micrite and more porous or sparry crystalline calcites. These alternating laminae have been interpreted to represent seasonally controlled differences in the biotic activity of microbes, and/or seasonally controlled changes in the rate of calcification. Either way, couplets of these microbially mediated alternating calcified laminae are generally agreed to represent annual seasonality. Combined stable isotope (δ18O and δ13C) and trace element (Mg, Sr, Ba) geochemistry from Recent tufa stromatolites show that seasonal climatic information is available from these calcites. Variability in δ18O (and in one case Mg concentration) has been shown to be controlled primarily by stream temperature change, usually driven by solar insolation. In arid climates, seasonal evaporation can also cause δ18O enrichment by at least 1‰. Variability in δ13C results potentially from: (1) seasonal change in plant uptake of 12C‐enriched CO2; (2) seasonal change in degassing of 12C‐enriched CO2 in the aquifer system; and (3) precipitation of calcite along the aquifer or river flow path, a process that increases δ13C of dissolved inorganic carbon (DIC) in the remaining water. Mechanisms 2 and 3 are linked because calcite precipitates in aquifers where degassing occurs, e.g. air pockets. The latter mechanism for δ13C enrichment has also been shown to cause sympathetic variation between trace element/Ca ratios and δ13C because trace elements with partition coefficients much greater than 1 (e.g. Sr, Ba) remain preferentially in solution. Since degassing in air pockets will be enhanced during decreased recharge when water saturation of the aquifer is lowest, sympathetic variation in trace element/Ca ratios and δ13C is a possible index of recharge and therefore precipitation intensity. High‐resolution geochemical data from well‐dated tufa stromatolites have great potential for Quaternary palaeoclimate reconstructions, possibly allowing recovery of annual seasonal climatic information including water temperature variation and change in rainfall intensity. However, careful consideration of diagenetic effects, particularly aggrading neomorphism, needs to be the next step. Copyright © 2005 John Wiley & Sons, Ltd.  相似文献   

6.
An amorphous or nanocrystalline calcium carbonate (ACC) phase with aragonite-like short-range order was found to be a transient precursor phase of calcite precipitation mediated by cyanobacteria of the strain Synechococcus leopoliensis PCC 7942. Using scanning transmission X-ray microscopy (STXM), different Ca-species such as calcite, aragonite-like CaCO3, and Ca adsorbed on extracellular polymers were discriminated and mapped, together with various organic compounds, at the 30 nm-scale. The nucleation of the amorphous aragonite-like CaCO3 was found to take place within the tightly bound extracellular polymeric substances (EPS) produced by the cyanobacteria very close to the cell wall. The aragonite-like CaCO3 is a type of ACC since it did not show either X-ray or electron diffraction peaks. The amount of aragonite-like CaCO3 precipitated in the EPS was dependent on the nutrient supply during bacterial growth. Higher nutrient concentrations (both N and P) during the cultivation of the cyanobacteria resulted in higher amounts of precipitation of the aragonite-like CaCO3, whereas the amount of Ca2+ adsorbed per volume of EPS was almost independent of the nutrient level. After the onset of the precipitation of the thermodynamically stable calcite and loss of supersaturation the aragonite-like CaCO3 dissolved whereas Ca2+ remained sorbed to the EPS albeit at lower concentrations. Based on these observations a model describing the temporal and spatial evolution of calcite nucleation on the surface of S. leopoliensis was developed. In another set of STXM experiments the amount of aragonite-like CaCO3 precipitated on the cell surface was found to depend on the culture growth phase: cells in the exponential growth phase adsorbed large amounts of Ca within the EPS and mediated nucleation of ACC, while cells at the stationary/death phase neither adsorbed large amounts of Ca2+ nor mediated the formation of aragonite-like CaCO3. It is suggested that precipitation of an X-ray amorphous CaCO3 layer by cyanobacteria could serve as a protection mechanism against uncontrolled precipitation of a thermodynamically stable phase calcite on their surface.  相似文献   

7.
《Sedimentology》2018,65(5):1611-1630
This study focuses on recent debate over the value of stable isotope‐based environmental proxies recorded in riverine tufa stromatolites. A twelve‐year record (1999 to 2012) of river‐bed tufa stromatolites in the River Piedra (north‐east Spain) was recovered in this study, along with a partly overlapping fifteen‐year record (1994 to 2009) of accumulations in a drainage pipe: both deposits formed in water with near identical physico/chemical parameters. Measured water temperature data and near‐constant δ 18Owater composition allowed selection of an ‘equilibrium’ palaeotemperature equation that best replicated actual temperatures. This study, as in some previous studies, found that just two published formulas for water temperature calculation from equilibrium calcite δ 18O compositions were appropriate for the River Piedra, where tufa deposition rates are high, with means between 5·6 mm and 10·8 mm in six months. The δ 18Ocalcite in both the river and the pipe deposits essentially records the full actual seasonal water temperature range. Only the coldest times (water temperature <10°C), when calcite precipitation mass decreased to minimum, are likely to be unrepresented, an effect most noticeable in the pipe where depositional masses are smaller and below sample resolution. While kinetic effects on δ 18Ocalcite‐based calculated water temperature cannot be ruled out, the good fit between measured water temperature and δ 18Ocalcite‐calculated water temperature indicates that temperature is the principal control. Textural and deposition rate variability between the river and pipe settings are caused by differences in flow velocity and illumination. In the river, calcification of growing cyanobacterial mat occurred throughout the year, producing composite dense and porous laminae, whereas in the pipe, discontinuous cyanobacterial growth in winter promoted more abiogenic calcification. High‐resolution δ 18Ocalcite data from synchronous pipe and river laminae show that reversals in water temperature occur within laminae, not at lamina boundaries, a pattern consistent with progressive increase in calcite precipitation rate as cyanobacterial growth re‐established in spring.  相似文献   

8.
The kinetics of calcite precipitation induced in response to the hydrolysis of urea by Bacillus pasteurii at different temperatures in artificial groundwater (AGW) was investigated. The hydrolysis of urea by B. pasteurii exhibited a temperature dependence with first order rate constants of 0.91 d−1 at 20°C, 0.18 d−1 at 15°C, and 0.09 d−1 at 10°C. At all temperatures, the pH of the AGW increased from 6.5 to 9.3 in less than 1 d. Dissolved Ca2+ concentrations decreased in an asymptotic fashion after 1 d at 20°C and 15°C, and 2 d at 10°C. The loss of Ca2+ from solution was accompanied by the development of solid phase precipitates that were identified as calcite by X-ray diffraction. The onset of calcite precipitation at each temperature occurred after similar amounts of urea were hydrolyzed, corresponding to 8.0 mM NH4+. Specific rate constants for calcite precipitation and critical saturation state were derived from time course data following a second-order chemical affinity-based rate law. The calcite precipitation rate constants and critical saturation states varied by less than 10% between the temperatures with mean values of 0.16 ± 0.01 μmoles L−1 d−1 and 73 ±3, respectively. The highest calcite precipitation rates (ca. 0.8 mmol L−1 d−1) occurred near the point of critical saturation. While unique time course trajectories of dissolved Ca2+ concentrations and saturation state values were observed at different temperatures, calcite precipitation rates all followed the same asymptotic profile decreasing with saturation state regardless of temperature. This emphasizes the fundamental kinetic dependence of calcite precipitation on saturation state, which connects the otherwise dissimilar temporal patterns of calcite precipitation that evolved under the different temperature and biogeochemical regimes of the experiments.  相似文献   

9.
Determining the relative proportions of silicate vs. carbonate weathering in the Himalaya is important for understanding atmospheric CO2 consumption rates and the temporal evolution of seawater Sr. However, recent studies have shown that major element mass-balance equations attribute less CO2 consumption to silicate weathering than methods utilizing Ca/Sr and 87Sr/86Sr mixing equations. To investigate this problem, we compiled literature data providing elemental and 87Sr/86Sr analyses for stream waters and bedrock from tributary watersheds throughout the Himalaya Mountains. In addition, carbonate system parameters (PCO2, mineral saturation states) were evaluated for a selected suite of stream waters. The apparent discrepancy between the dominant weathering source of dissolved major elements vs. Sr can be reconciled in terms of carbonate mineral equilibria. Himalayan streams are predominantly Ca2+-Mg2+-HCO3− waters derived from calcite and dolomite dissolution, and mass-balance calculations demonstrate that carbonate weathering contributes ∼87% and ∼76% of the dissolved Ca2+ and Sr2+, respectively. However, calculated Ca/Sr ratios for the carbonate weathering flux are much lower than values observed in carbonate bedrock, suggesting that these divalent cations do not behave conservatively during stream mixing over large temperature and PCO2 gradients in the Himalaya.The state of calcite and dolomite saturation was evaluated across these gradients, and the data show that upon descending through the Himalaya, ∼50% of the streams evaluated become highly supersaturated with respect to calcite as waters warm and degas CO2. Stream water Ca/Mg and Ca/Sr ratios decrease as the degree of supersaturation with respect to calcite increases, and Mg2+, Ca2+, and HCO3− mass balances support interpretations of preferential Ca2+ removal by calcite precipitation. On the basis of patterns of saturation state and PCO2 changes, calcite precipitation was estimated to remove up to ∼70% of the Ca2+ originally derived from carbonate weathering. Accounting for the nonconservative behavior of Ca2+ during riverine transport brings the Ca/Sr and 87Sr/86Sr composition of the carbonate weathering flux into agreement with the composition of carbonate bedrock, thereby permitting consistency between elemental and Sr isotope approaches to partitioning stream water solute sources. These results resolve the dissolved Sr2+ budget and suggest that the conventional application of two-component Ca/Sr and 87Sr/86Sr mixing equations has overestimated silicate-derived Sr2+ and HCO3− fluxes from the Himalaya. In addition, these findings demonstrate that integrating stream water carbonate mineral equilibria, divalent cation compositional trends, and Sr isotope inventories provides a powerful approach for examining weathering fluxes.  相似文献   

10.
Holocene stromatolites are described from Lake Walyungup, a coastal hyposaline lake in south-western Australia. At summer low water, this groundwater-fed depression comprises two permanent shallow water bodies and an ephemeral southern pool, set within an areally extensive littoral zone of variably cemented carbonate crust. Up to 5 m of organic-rich carbonate mud has been deposited within each of these basins in less than 7000 years. Stromatolites rim the water bodies with individual columns up to 2 m tall. Stromatolite-capped tepee structures in subparallel alignment are widespread in the littoral crust, suggesting a linkage between stromatolite growth and zones of groundwater discharge. Lake Walyungup stromatolites, regardless of external morphology and setting, are coarsely laminated and have aragonitic mesoclot microfabrics. These microfabrics are similar to those from lithified portions of active thrombolitic microbialites from nearby Lake Clifton. Hydromagnesite is a minor to subdominant phase (up to 47 wt%) of the carbonate mineral assemblage in Lake Walyungup. It occurs mainly in the littoral zone as a diagenetic replacement of precursor aragonite, particularly within the mesoclot fabric of stromatolites, but also in sediments (strandline and dune sand, crusts) derived mainly from erosion of stromatolites. In contrast with nonreplaced and impermeable inorganic aragonitic cements, stromatolite mesoclots are microper- meable. Micropermeability is inferred to facilitate hydromagnesite diagenesis. Dolomite is also present in minor amounts as a pore fill in stromatolites, and as a subdominant to dominant (up to 100 wt%) phase in thin, mudcracked micrite layers within the crust package. The layered dolomite may be precipitated directly from the lake water. Major element abundance of the lake water is: Na+ > Mg2+ » K+ > Ca2+ for cations, and Cl? » SO42? ≈ HCO3? > CO32? for anions. Compared to other nearby coastal lakes, Lake Walyungup has a high pH (> 9·0), and an extremely high molar Mg/Ca ratio of > 90. Groundwater in the area has a Mg/Ca ratio generally less than 1. The unusual Mg/Ca ratio in Lake Walyungup is partially a result of in-lake processes with additional minor contribution of Mg2+ sourced from basal marine sand because no Mg-rich bedrock source has been found in the region.  相似文献   

11.
This study assesses the potential use of Mg isotopes to trace Mg carbonate precipitation in natural waters. Salda Lake (SW Turkey) was chosen for this study because it is one of the few modern environments where hydrous Mg carbonates are the dominant precipitating minerals. Stromatolites, consisting mainly of hydromagnesite, are abundant in this lake. The Mg isotope composition of incoming streams, groundwaters, lake waters, stromatolites, and hydromagnesite-rich sediments were measured. Because Salda Lake is located in a closed basin, mass balance requires that the Mg isotopic offset between Lake Salda water and precipitated hydromagnesite be comparable to the corresponding offset between Salda Lake and its water inputs. This is consistent with observations; a ??26Mg offset of 0.8?C1.4??? is observed between Salda Lake water and it is the incoming streams and groundwaters, and precipitated hydromagnesite has a ??26Mg 0.9?C1.1??? more negative than its corresponding fluid phase. This isotopic offset also matches closely that measured in the laboratory during both biotic and abiotic hydrous Mg carbonate precipitation by cyanobacteria (Mavromatis, V., Pearce, C., Shirokova, L. S., Bundeleva, I. A., Pokrovsky, O. S., Benezeth, P. and Oelkers, E.H.: Magnesium isotope fractionation during inorganic and cyanobacteria-induced hydrous magnesium carbonate precipitation, Geochim. Cosmochim. Acta, 2012a. 76, 161?C174). Batch reactor experiments performed in the presence of Salda Lake cyanobacteria and stromatolites resulted in the precipitation of dypingite (Mg5(CO3)4(OH)2·5(H2O)) and hydromagnesite (Mg5(CO3)4(OH)2·4H2O) with morphological features similar to those of natural samples. Concurrent abiotic control experiments did not exhibit carbonate precipitation demonstrating the critical role of cyanobacteria in the precipitation process.  相似文献   

12.
Microbialites (benthic microbial carbonate deposits) were discovered in a hypersaline alkaline lake on Eleuthera Island (Bahamas). From the edge towards the centre of the lake, four main zones of precipitation could be distinguished: (1) millimetre‐sized clumps of Mg‐calcite on a thin microbial mat; (2) thicker and continuous carbonate crusts with columnar morphologies; (3) isolated patches of carbonate crust separated by a dark non‐calcified gelatinous mat; and (4) a dark microbial mat without precipitation. In thin section, the precipitate displayed a micropeloidal structure characterized by micritic micropeloids (strong autofluorescence) surrounded by microspar and spar cement (no fluorescence). Observations using scanning electron microscopy (SEM) equipped with a cryotransfer system indicate that micrite nucleation is initiated within a polymer biofilm that embeds microbial communities. These extracellular polymeric substances (EPS) are progressively replaced with high‐Mg calcite. Discontinuous EPS calcification generates a micropeloidal structure of the micrite, possibly resulting from the presence of clusters of coccoid or remnants of filamentous bacteria. At high magnification, the microstructure of the initial precipitate consists of 200–500 nm spheres. No precipitation is observed in or on the sheaths of cyanobacteria, and only a negligible amount of precipitation is directly associated with the well‐organized and active filamentous cyanobacteria (in deeper layers of the mat), indicating that carbonate precipitation is not associated with CO2 uptake during photosynthesis. Instead, the precipitation occurs at the uppermost layer of the mat, which is composed of EPS, empty filamentous bacteria and coccoids (Gloeocapsa spp.). Two‐dimensional mapping of sulphate reduction shows high activity in close association with the carbonate precipitate at the top of the microbial mat. In combination, these findings suggest that net precipitation of calcium carbonate results from a temporal and spatial decoupling of the various microbial metabolic processes responsible for CaCO3 precipitation and dissolution. Theoretically, partial degradation of EPS by aerobic heterotrophs or UV fuels sulphate‐reducing activity, which increases alkalinity in microdomains, inducing CaCO3 precipitation. This degradation could also be responsible for EPS decarboxylation, which eliminates Ca2+‐binding capacity of the EPS and releases Ca2+ ions that were originally bound by carboxyl groups. At the end of these processes, the EPS biofilm is calcified and exhibits a micritic micropeloidal structure. The EPS‐free precipitate subsequently serves as a substrate for physico‐chemical precipitation of spar cement from the alkaline water of the lake. The micropeloidal structure has an intimate mixture of micrite and microspar comparable to microstructures of some fossil microbialites.  相似文献   

13.
Tufa samples from 16 consecutive barrages along a 13 km section of the groundwater‐fed Krka River (Slovenia) were analysed for their petrographical, mineralogical, elemental and stable carbon (δ13C) and oxygen (δ18O) isotope composition, to establish their relation to current climatic and hydrological conditions. Waters constantly oversaturated with calcite and the steep morphology of the Krka riverbed stimulate rapid CO2 degassing and subsequent tufa precipitation. The carbon isotope fractionation (Δ13C) between dissolved inorganic carbon and tufa in the Krka River evolves towards isotopic equilibrium being controlled by continuous CO2 degassing and tufa precipitation rate downstream. The Δ13C increased from 1·9 to 2·5‰ (VPDB); however, since tufa precipitation rates remain similar downstream, the major controlling factor of carbon isotope exchange is most probably related to the continuous 12CO2 degassing downstream leaving the carbon pool enriched in 13C. In the case of oxygen, the isotope fractionation (Δ18O) was found to be from 1·0 to 2·3‰ (VSMOW) smaller than reported in the literature. The observed discrepancies are due to different precipitation rates of calcite deposits because Krka tufas on cascades grow relatively faster compared to slowly precipitated calcite deposits in cave or stream pools. Due to non‐equilibrium oxygen isotope exchange between Krka tufa and water, the δ18O proxy showed from 1·2 to 8·2°C higher calculated water temperatures compared to measured water temperatures, demonstrating that δ18O proxy‐based temperature equations are not reliable for water temperature calculations of fast‐growing tufa on cascades. Because Mg is bound to the terrigenous dolomite fraction in the Krka tufa samples, the Mg/Ca was also found to be an unreliable temperature proxy yielding over up to 20°C higher calculated water temperatures.  相似文献   

14.
Fossil stromatolites may reveal information about their hydrochemical palaeoenvironment, provided that assignment to a specific microbial community and a corresponding biogeochemical mechanism of formation can be made. Tithonian stromatolites of the Münder Formation at Thüste, north Germany, have traditionally been considered as formed by intertidal cyanobacterial communities. However, thin sections of the stromatolites show elongated angular traces of former gypsum crystals in a dense arrangement, but no algal or cyanobacterial filament traces. Moreover, high Fe2+ and Mn2+ contents, oxygen‐isotope and sulphur‐isotope ratios of carbonate‐bound sulphates, and sulphurized hydrocarbon biomarkers of the stromatolitic carbonate indicate that CaCO3 precipitation occurred near the oxic–anoxic interface as a result of intensive bacterial sulphur cycling rather than photosynthetic activity. Furthermore, anaerobic oxidation of methane by Archaea may have driven CaCO3 precipitation in deeper parts of the biofilm community, as reflected by high concentrations of squalane with a strongly negative δ13C in conjunction with evaporite pseudomorphs showing extremely low δ13CCarb ratios. Consequently, the Thüste stromatolites are now interpreted as having initially formed by gypsum impregnation of biofilms. Subsequently, early Mg‐calcitic calcitization within the biofilms occurred because of combined bacterial iron, manganese and sulphate reduction, with an increasing contribution of anaerobic oxidation of methane with depth. This model plausibly explains the prominent preservation of signals derived from oxygen‐independent metabolic pathways, whereas virtually no geochemical record exists for an aerobic community that may, nevertheless, have prevailed at the stromatolite surface. Photic‐zone stromatolites with a prominent signal of anaerobic oxidation of methane may be common in, and indicative of, oxygen‐depleted sulphate‐bearing environments with high rates of methane production, conditions that possibly were fulfilled at the Archaean to Proterozoic transition.  相似文献   

15.
Three types of recent carbonate precipitates from the River Krka, Croatia, were analysed: (1) bulk tufa from four main cascades in a 34 km long section of the river flow through the Krka National Park; (2) a laminar stromatolite‐like incrustation formed in the tunnel of a hydroelectric power plant close to the lowest cascade; and (3) recent precipitates collected on artificial substrates during winter, spring and summer periods. Stable isotope compositions of carbon (δ13C) and oxygen (δ18O) in the carbonate and organic carbon (δ13Corg) were determined and compared with δ18O of water and δ13C of dissolved inorganic carbon (DIC). The source of DIC, which provides C for tufa precipitation, was determined from the slope of the line ([DIC]/[DIC0]?1) vs. (δ13C‐DIC × ([DIC]/[DIC0])) ( Sayles & Curry, 1988 ). The δ13C value of added DIC was ?13·6‰, corresponding to the dissolution of CO2 with δ13C between ?19·5 and ?23·0‰ Vienna Pee Dee Belemnite (VPDB). The observed difference between the measured and calculated equilibrium temperature of precipitation of bulk tufa barriers indicates that the higher the water temperature, the larger the error in the estimated temperature of precipitation. This implies that the climatic signals may be valid only in tufas precipitated at lower and relatively stable temperatures. The laminar crust comprising a continuous record of the last 40 years of precipitation shows a consistent trend of increasing δ13C and decreasing δ18O. The lack of covariation between δ13C and δ18O indicates that precipitation of calcite was not kinetically controlled for either of the elements. δ13C and δ18O of precipitates collected on different artificial substrates show that surface characteristics both of substrates and colonizing biota play an important role in C and O isotope fractionation during carbonate precipitation.  相似文献   

16.
Hydrochemical studies of the Plitvice Lakes and their tributaries (Croatia/Yugoslavia) were coupled with micromorphological investigations on carbonate lake sediments and recent travertines. Karst springs discharge water from aquifers in Triassic and Jurassic dolomites and limestones and collect in lakes, which are ponded behind accreting travertine dams. Waters at springs have a high CO2 partial-pressure (greater than 7000 ppm) and are slightly undersaturated with respect to calcite (saturation index less than —0·03). CO2 partial pressure is quickly reduced in swift running streams, leading to very high supersaturation with carbonate minerals (saturation indices between 0·74 and 0·53). Calcite deposition, however, is restricted to the lake bottoms (formation of lake marl) and to the tufa dams. The annual carbonate precipitating capacity of the system based on water balance and downstream loss of dissolved ions is estimated to be on the order of 10 000 t CaCO3 as cascade deposits (tufa dams) or as micrite in lakes behind the travertine dams. The initial stages of travertine formation as a result of morphological, biological, and chemical factors are (i) moss settling on small ridges in the creek courses, (ii) epiphytes (diatoms and cyanobacteria) settling on the moss surface, (iii) micrite particles resuspending from lake bottoms and being trapped on mucous excretions from bacteria and diatoms, and (iv) inorganic calcite precipitating as sparite at nucleation sites provided by these crystal seeds. Geochemical studies of the lake marl and tufa dams show that amino acids are dominated by aspartic acid. Carbohydrates come from structural polysaccharides of diatoms. The sticky excretions, rich in aspartic acid, are necessary for the initiation of calcite precipitation. They may be a response of algal and bacterial metabolism to environmental stress by either nutrient depletion or high calcium concentrations in ambient waters. The formation of tufa and micrite (lake marl) appears to be initiated by localized biological factors and is not governed by mere calcite supersaturation of the water. Oligotrophy may be an essential precondition for the formation of fresh water carbonate deposits.  相似文献   

17.
Calcareous stromatolites of the upper Siyeh Limestone (ca. 1.1 ° 109 years old) were studied in the central part of Glacier National Park, Montana. The stromatolites, mound- and dome-shaped structures deposited in a shallow, generally submerged, tidally influenced setting, were formed by a combination of in situ carbonate precipitation and organic stabilization of detrital material. Well-developed, 1–4 cm diameter, branched columns occur in a single stromatolite bed.Physical factors, including the size and shape of sediment-surface irregularities upon which the stromatolites developed, the rate of sedimentation between stromatolites, and the water depth, played a major role in controlling stromatolite macrostructure. Deposition of non-organically stabilized detritus on stromatolite growth surfaces inhibited the development of small-diameter columns by smoothing over developing growth features. Columnar structures are absent in stromatolites that contain abundant non-organically stabilized sediment. In contrast, they are well-developed in a stromatolite bed that is relatively deficient in such material.“Molar-tooth” structures are common in the impure dolomitic limestones, and the abundant sheet-shaped forms appear to be sparry-calcite-filled syneresis cracks.  相似文献   

18.
The microboring activity of endolithic cyanobacteria plays a major role in the formation of the dominant lithified laminae in modern marine stromatolites in the Exuma Cays, Bahamas. These stromatolites are composed primarily of fine-grained carbonate sand that is trapped and bound by the filamentous cyanobacteria Schizothrix sp.. Periodic introduction of coccoid endolithic cyanobacteria Solentia sp. during hiatuses in stromatolite growth associated with very low rates of sedimentation results in the formation of lithified horizons, 200–1000 μm thick. These layers consist of micritized grains that are welded together at point contacts. The micritization is caused by extensive microboring and carbonate precipitation within boreholes concurrent with endolithic activity. Grain welding occurs when boreholes cross from one grain to another at point contacts. Thus, microboring destroys original grain textures but, at the same time, plays a constructional role in stromatolite growth by forming lithified layers of welded grains. These lateral bands of fused carbonate grains help to stabilize and preserve the stromatolite deposits.  相似文献   

19.
Physiochemical controls on the carbonate geochemistry of large river systems are important regulators of carbon exchange between terrestrial and marine reservoirs on human time scales. Although many studies have focused on large-scale river carbon fluxes, there are few investigations of mechanistic aspects of carbonate mass balance and transport at the catchment scale. We determined elemental and carbonate geochemistry and mass balances for net carbonate dissolution fluxes from the forested, mid-latitude Huron River watershed, established on carbonate-rich unconfined glacial drift aquifers. Shallow groundwaters are near equilibrium with respect to calcite at pCO2 values up to 25 times atmospheric values. Surface waters are largely groundwater fed and exhibit chemical evolution due to CO2 degassing, carbonate precipitation in lakes and wetlands, and anthropogenic introduction of road salts (NaCl and CaCl2). Because the source groundwater Mg2+/HCO3 ? ratio is fairly constant, this parameter permits mass balances to be made between carbonate dissolution and back precipitation after groundwater discharge. Typically, precipitation does not occur until IAP/K calcite values exceed 10 times supersaturation. Stream chemistry changes little thereafter even though streams remain highly supersaturated for calcite. Our data taken together with historical United States Geological Survey (USGS) data show that alkalinity losses to carbonate precipitation are most significant during periods of lowest discharge. Thus, on an annual basis, the large carbon flux from carbonate dissolution in soil zones is only decreased by a relatively small amount by the back precipitation of calcium carbonate.  相似文献   

20.
A relict mound of Holocene barite (BaSO4) tufa underlies the Flybye Springs, a small, barium‐rich, cold sulphur spring system in the Northwest Territories of Canada. The tufa is composed of relatively pure barite with ≤0·34 wt% Ca2+ and ≤0·77 wt% Sr2+. The mound is made up of coated bubble, raft, undulatory sheet, stromatolitic, coated grain and detrital conglomerate barite tufa. Although previously unreported in barite, these lithotypes are akin to facies found in many carbonate spring deposits. Raft and ooid‐coated grain tufa was formed via ‘inorganic’ barite precipitation in spring water ponds and tributaries where rapid oxidation of sulphide to sulphate established barite supersaturation. Undulatory sheet tufa may have formed by the reaction of dissolved barium with sulphate derived from the oxidation of extracellular polysaccharide‐rich colloidal sulphur films floating in oxygenated, barite‐saturated spring water ponds. Coated bubble, oncoid‐coated grain and stromatolitic tufa with filamentous microfossils was formed in close association with sulphur‐tolerant microbes inhabiting dysoxic and oxygenated spring water tributaries and ponds. Adsorption of dissolved barium to microbial extracellular polysaccharide probably facilitated the development of these ‘biogenic’ lithotypes. Detrital conglomerate tufa was formed by barite cementation of microdetrital tufa, allochthonous lithoclasts and organic detritus, including caribou hair. Biogenic textures, organic artefacts and microfossils in the Flybye barite tufa have survived diagenetic aggradational recrystallization and precipitation of secondary cements, indicating the potential for palaeoecological information to be preserved in barite in the geological record. Similarities between the Flybye barite tufa and carbonate spring deposits demonstrate that analogous textures can develop in chemical sedimentary systems with distinct mineralogy, biology and physiochemistry.  相似文献   

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