Biomediated Precipitation of Calcium Carbonate in a Slightly Acidic Hot Spring, Yunnan Province

A slightly acidic hot spring named "Female Tower"(t=73.5°C, pH=6.64) is located in the Jifei Geothermal Field, Yunnan Province, southwestern China. The precipitates in the hot spring are composed of large amounts of calcite, aragonite and sulfur. Scanning electron microscopy(SEM) analyses reveal that the microbial mats were formed from various coccoid or rod-shaped filamentous microbes. Transmission electron microscopy(TEM) shows that the intracellular sulfur granules are commonly associated with these microbes. A culture-independent molecular phylogenetic analysis demonstrates that the majority of the bacteria in the spring are sulfur-oxidizing bacteria. In the spring water, H_2S concentration is up to 60 ppm, while SO_4~(2-) concentration is only about 10 ppm. We speculate that H_2S might derive from sulfur-oxidizing bacteria in this hot spring water, leading to the intracellular formation of sulfur granules. Meanwhile, this reaction increased the p H in the micronscale microdomains, which fosters the precipitation of calcium carbonate in the microbial mats. The results of this study indicate that the sulfur-oxidizing bacteria might play an important role in calcium carbonate precipitation in slightly acidic hot spring environments.     

Stromatolitic fabric of authigenic carbonate crusts: result of anaerobic methane oxidation at cold seeps in 4,850 m water depth

Methane seepage leads to Mg-calcite and aragonite precipitation at a depth of 4,850 m on the Aleutian accretionary margin. Stromatolitic and oncoid growth structures imply encrustation of microorganisms (microbial mats) in the host sediment with a unique growth direction downward into the sediment, forming crust-shaped lithologies. Biomarker investigations of the residue after carbonate dissolution show strong enrichments in crocetane and archaeol, which contain extremely low '¹³C values. This indicates the presence of methane-consuming archaea, and '¹³C values of -42 to -51‰ PDB indicate that methane is the carbon source for the carbonate crusts. Thus, it appears that stromatolitic encrustations of methanotrophic anaerobic archaea probably occurs in a consortium with sulphate-reducing bacteria and that carbonate precipitation proceeds downward into the sediment, where ascending cold fluids provide a methane source. Strontium and oxygen isotope analyses as well as ¹⁴C ages of the carbonates suggest that the fluids come from deep within the sediment and that carbonate precipitation began about 3,000 years ago.     

Balancing the Oceanic Calcium Carbonate Cycle: Consequences of Variable Water Column ��

The paired chemical reactions, Ca²⁺ + 2HCO₃ ^? ? CaCO₃ + CO₂ + H₂O, overestimate the ratio of CO₂ flux to CaCO₃ flux during the precipitation or dissolution of CaCO₃ in seawater. This ratio, which has been termed ??, is about 0.6 in surface seawater at 25°C and at equilibrium with contemporary atmospheric CO₂ and increases towards 1.0 as seawater cools and pCO₂ increases. These conclusions are based on field observations, laboratory experiments, and equilibrium calculations for the seawater carbonate system. Yet global geochemical modeling indicates that small departures of ?? from 1.0 would cause dramatic, rapid, and unrealistic change in atmospheric CO₂. ?? can be meaningfully calculated for a water sample whether or not it is in equilibrium with the atmosphere. The analysis presented here demonstrates that the atmospheric CO₂ balance can be maintained constant with respect to seawater CaCO₃ reactions if one considers the difference between CaCO₃ precipitation and burial and differing values for ?? (both <1.0) in regions of precipitation and dissolution within the ocean.     

Seasonal Variability of Mineral Formation in Microbial Mats Subjected to Drying and Wetting Cycles in Alkaline and Hypersaline Sedimentary Environments

Interactions of the microbial mat community with the sedimentary environment were evaluated in two shallow, ephemeral lakes with markedly different hydrochemistry and mineralogy. The characterization of growing and decaying microbial mats by light microscopy observations and fluorescence in situ hybridization was complemented with biogeochemical and mineralogical measurements. The lakes studied were Eras and Altillo Chica, both located in Central Spain and representing poly-extreme environments. Lake Eras is a highly alkaline, brackish to saline lake containing a high concentration of chloride, and in which the carbonate concentration exceeds the sulfate concentration. The presence of magnesium is crucial for the precipitation of hydromagnesite in microbialites of this lake. Altillo Chica is a mesosaline to hypersaline playa lake with high concentrations of sulfate and chloride, favoring the formation of gypsum microbialites. Differences in the microbial community composition and mineralogy of the microbialites between the two lakes were primarily controlled by alkalinity and salinity. Lake Eras was dominated by the cyanobacterial genus Oscillatoria, as well as Alphaproteobacteria, Gammaproteobacteria and Firmicutes. When the mat decayed, Alphaproteobacteria and Deltaproteobacteria increased and became the dominant heterotrophs, as opposed to Firmicutes. In contrast, Deltaproteobacteria was the most abundant group in Lake Altillo Chica, where desiccation led to mats decay during evaporite formation. In addition to Deltaproteobacteria, Cyanobacteria, Actinobacteria, Alphaproteobacteria and Gammaproteobacteria were found in Altillo Chica, mostly during microbial mats growth. At both sites, microbial mats favored the precipitation of sulfate and carbonate minerals. The precipitation of carbonate is higher in the soda lake due to a stronger alkalinity engine and probably a higher degradation rate of exopolymeric substances. Our findings clarify the distribution patterns of microbial community composition in ephemeral lakes at the levels of whole communities, which were subjected to environmental conditions similar to those that may have existed during early Earth.     

External controls on the distribution,fabrics and mineralization of modern microbial mats in a coastal hypersaline lagoon,Cayo Coco (Cuba)

Active, carbonate‐mineralizing microbial mats flourish in a tropical, highly evaporative, marine‐fed lagoonal network to the south of Cayo Coco Island (Cuba). Hypersaline conditions support the development of a complex sedimentary microbial ecosystem with diverse morphologies, a variable intensity of mineralization and a potential for preservation. In this study, the role of intrinsic (i.e. microbial) and extrinsic (i.e. physicochemical) controls on microbial mat development, mineralization and preservation was investigated. The network consists of lagoons, forming in the interdune depressions of a Pleistocene aeolian substratum; they developed due to a progressive increase in sea‐level since the Holocene. The hydrological budget in the Cayo Coco lagoonal network changes from west to east, increasing the salinity. This change progressively excludes grazers and increases the saturation index of carbonate minerals, favouring the development and mineralization of microbial mats in the easternmost lagoons. Detailed mapping of the easternmost lagoon shows four zones with different flooding regimes. The microbial activity in the mats was recorded using light–dark shifts in conjunction with microelectrode O₂ and HS^? profiles. High rates of O₂ production and consumption, in addition to substantial amounts of exopolymeric substances, are indicative of a potentially strong intrinsic control on mineralization. Seasonal, climate‐driven water fluctuations are key for mat development, mineralization, morphology and distribution. Microbial mats show no mineralization in the permanently submersed zone, and moderate mineralization in zones with alternating immersion and exposure. It is suggested that mineralization is also driven by water‐level fluctuations and evaporation. Mineralized mats are laminated and consist of alternating trapping and binding of grains and microbially induced magnesium calcite and dolomite precipitation. The macrofabrics of the mats evolve from early colonizing Flat mats to complex Cerebroid or Terrace structures. The macrofabrics are influenced by the hydrodynamic regime: wind‐driven waves inducing relief terraces in windward areas and flat morphologies on the leeward side of the lagoon. Other external drivers include: (i) storm events that either promote (for example, by bioclasts covering) or prevent (for example, by causing erosion) microbial mat preservation; and (ii) subsurface degassing, through mangrove roots and desiccation cracks covered by Flat mats (i.e. forming Hemispheroids and Cerebroidal structures). These findings provide in‐depth insights into understanding fossil microbialite morphologies that formed in lagoonal settings.     

Changes of the chemical composition of discharged coal mine water in the Rontok Pond, Upper Silesia, Poland

 The natural process of sulphate reduction takes place in the Rontok Pond. During the reduction the concentration of sulphate in the pond water decreases. The changes of δ³⁴S in the pond water are typical for bacterial reduction. The reduction process in the Rontok Pond causes dissolution of barium and the radium from the pond sediments into the water. Concentrations of barium and ²²⁶Ra in the discharged water from the Silesia Coal Mine are lower than in water flowing out of the Rontok Pond into the Vistula River. The opposite trend is observed for iron and also Zn, Co, Ni, Mn, Al and Cu because of the precipitation of ferric hydroxide in the stream. The reduction process, which causes dissolution of barium and radium in water, can explain the release of these elements into the Vistula River. The dissolution of toxic elements can be reduced by the precipitation of non-toxic deposits on the sediment of Rontok Pond. Received: 3 July 1999 · Accepted: 27 March 2000     

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.     

Hydrogeochemical Analysis of Processes Through Modeling of Seawater Intrusion Impacts in Biscayne Aquifer Water Quality,USA

Hydrogeochemical processes that accompany seawater intrusion in coastal aquifers can alter the resulting water quality and are important ingredients in coastal aquifer management. The presence of dissolution–precipitation reactions and ion exchange in the mixing zone of the Biscayne aquifer (FL, USA) are suggested based on changes in major ion concentrations and mineral saturation indices (SI). Major ion concentrations from 11 groundwater samples are compared with theoretical mixing between freshwater and seawater. PHREEQC code was used to calculate saturation indices of the samples with respect to common phases in the Biscayne aquifer. High Ca²⁺ and HCO₃ ^? content of the samples is typical of waters in contact with carbonate aquifers. Water quality of the samples is mainly attributed to mixing and precipitation–dissolution reactions with calcite and dolomite. The samples were saturated with calcite (SI ~ 0) and undersaturated for dolomite (SI < 0), while a few samples showed dolomite saturation. Because gypsum and halite SI could be predicted by theoretical mixing, reactions with those minerals, if present, are thought to be insignificant. In the active intrusion areas, cation exchange also appears to modify water quality leading to excess Ca²⁺, but depleted Na⁺, Mg²⁺ and K⁺ concentrations. On the other hand, samples from previous intrusion areas plotted very close to the theoretical mixing line and approached equilibrium with the seawater.     

Geochemical and mineralogical aspects of sulfide mine tailings

Tailings generated during processing of sulfide ores represent a substantial risk to water resources. The oxidation of sulfide minerals within tailings deposits can generate low-quality water containing elevated concentrations of SO₄, Fe, and associated metal(loid)s. Acid generated during the oxidation of pyrite [FeS₂], pyrrhotite [Fe_(1−x)S] and other sulfide minerals is neutralized to varying degrees by the dissolution of carbonate, (oxy)hydroxide, and silicate minerals. The extent of acid neutralization and, therefore, pore-water pH is a principal control on the mobility of sulfide-oxidation products within tailings deposits. Metals including Fe(III), Cu, Zn, and Ni often occur at high concentrations and exhibit greater mobility at low pH characteristic of acid mine drainage (AMD). In contrast, (hydr)oxyanion-forming elements including As, Sb, Se, and Mo commonly exhibit greater mobility at circumneutral pH associated with neutral mine drainage (NMD). These differences in mobility largely result from the pH-dependence of mineral precipitation–dissolution and sorption–desorption reactions. Cemented layers of secondary (oxy)hydroxide and (hydroxy)sulfate minerals, referred to as hardpans, may promote attenuation of sulfide-mineral oxidation products within and below the oxidation zone. Hardpans may also limit oxygen ingress and pore-water migration within sulfide tailings deposits. Reduction–oxidation (redox) processes are another important control on metal(loid) mobility within sulfide tailings deposits. Reductive dissolution or transformation of secondary (oxy)hydroxide phases can enhance Fe, Mn, and As mobility within sulfide tailings. Production of H₂S via microbial sulfate reduction may promote attenuation of sulfide-oxidation products, including Fe, Zn, Ni, and Tl, via metal-sulfide precipitation. Understanding the dynamics of these interrelated geochemical and mineralogical processes is critical for anticipating and managing water quality associated with sulfide mine tailings.     

The lacustrine microbial carbonate factory of the successive Lake Bonneville and Great Salt Lake,Utah, USA

The Bonneville Basin is a continental lacustrine system accommodating extensive microbial carbonate deposits corresponding to two distinct phases: the deep Lake Bonneville (30 000 to 11 500 ¹⁴C bp ) and the shallow Great Salt Lake (since 11 500 ¹⁴C bp ). A characterization of these microbial deposits and their associated sediments provides insights into their spatio‐temporal distribution patterns. The Bonneville phase preferentially displays vertical distribution of the microbial deposits resulting from high‐amplitude lake level variations. Due to the basin physiography, the microbial deposits were restricted to a narrow shoreline belt following Bonneville lake level variations. Carbonate production was more efficient during intervals of relative lake level stability as recorded by the formation of successive terraces. In contrast, the Great Salt Lake microbial deposits showed a great lateral distribution, linked to the modern flat bottom configuration. A low vertical distribution of the microbial deposits was the result of the shallow water depth combined with a low amplitude of lake level fluctuations. These younger microbial deposits display a higher diversity of fabrics and sizes. They are distributed along an extensive ‘shore to lake’ transect on a flat platform in relation to local and progressive accommodation space changes. Microbial deposits are temporally discontinuous throughout the lake history showing longer hiatuses during the Bonneville phase. The main parameters controlling the rate of carbonate production are related to the interaction between physical (kinetics of the mineral precipitation, lake water temperature and runoff), chemical (Ca²⁺, Mg²⁺ and HCO₃^? concentrations, Mg/Ca ratio, dilution and depletion) and/or biological (trophic) factors. The contrast in evolution of Lake Bonneville and Great Salt Lake microbial deposits during their lacustrine history leads to discussions on major chemical and climatic changes during this interval as well as the role of physiography. Furthermore, it provides novel insights into the composition, structure and formation of microbialite‐rich carbonate deposits under freshwater and hypersaline conditions.     

Hydrogen sulfide and organic carbon at the sediment–water interface in coastal brackish Lake Nakaumi, SW Japan

The relationship among H₂S, total organic carbon (TOC), total sulfur (TS) and total nitrogen contents of surface sediments (0–1 cm) was examined to quantify the relationship between H₂S concentrations and TOC content at the sediment water interface in a coastal brackish lake, Nakaumi, southwest Japan. In this lake, bottom water becomes anoxic during summer due to a strong halocline. Lake water has ample dissolved SO₄ ^2? and the surface sediments are rich in planktic organic matter (C/N 7–9), which is highly reactive in terms of sulfate reduction. In this setting the amount of TOC should be a critical factor regulating the activity of sulfate reduction and H₂S production. In portions of the lake where sediment TOC content is less than 3.5 %, H₂S was very low or absent in both bottom and pore waters. However, in areas with TOC >3.5 %, H₂S was correlated with TOC content (pore water H₂S (ppm) = 13.9 × TOC (%) ? 52.1, correlation coefficient: 0.72). H₂S was also present in areas with sediment TS above 1.2 % (present as iron sulfide), which suggests that iron sulfide formation is tied to the amount of TOC. Based on this relationship, H₂S production has progressively increased after the initiation of land reclamation projects in Lake Nakaumi, as the area of sapropel sediments has significantly increased. This TOC–H₂S relationship at sediment–water interface might be used to infer H₂S production in brackish–lagoonal systems similar to Lake Nakaumi, with readily available SO₄ ^2? and reactive organic matter.     

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

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

Hydrothermal mixing,carbonate dissolution and sulfide precipitation in Mississippi Valley-type deposits

A large number of Mississippi Valley-Type (MVT) deposits are located within dissolution zones in carbonate host rocks. Some genetic models propose the existence of cavities generated by an earlier event such as a shallow karstification, that were subsequently filled with hydrothermal minerals. Alternative models propose carbonate dissolution caused by the simultaneous precipitation of sulfides. These models fail to explain either the deep geological setting of the cavities, or the observational features which suggest that the dissolution of carbonates and the precipitation of minerals filling the cavities are not strictly coeval. We present a genetic model inspired by the textural characteristics of MVT deposits that accounts for both the dissolution of carbonate and precipitation of sulfides and later carbonates in variable volumes. The model is based on the mixing of two hydrothermal fluids with a different chemistry. Depending on the proportion of the end members, the mixture dissolves and precipitates carbonates even though the two mixing solutions are both independently saturated in carbonates. We perform reactive transport simulations of mixing of a regional groundwater and brine ascending through a fracture, both saturated in calcite, but with different overall chemistries (Ca and carbonate concentrations, pH, etc). As a result of the intrinsic effects of chemical mixing, a carbonate dissolution zone, which is enhanced by acid brines, appears above the fracture, and another zone of calcite precipitation builds up between the cavity and the surrounding rock. Sulfide forms near the fracture and occupies a volume smaller than the cavity. A decline of the fluid flux in the fracture would cause the precipitation of calcite within the previously formed cavities. Therefore, dissolution of carbonate host rock, sulfide precipitation within the forming cavity, and later filling by carbonates may be part of the same overall process of mixing of fluids in the carbonate host rock.Editorial handling: C. Everett     

Lipid biomarker analysis of cyanobacteria-dominated microbial mats in meltwater ponds on the McMurdo Ice Shelf,Antarctica

The lipid biomarker composition of microbial mat communities from three meltwater ponds from the McMurdo Ice Shelf, Antarctica, was investigated for the first time. Hydrocarbons, ether-linked components, fatty acids (FAs), wax esters, hopanols and sterols from Fresh, Orange and Salt Ponds were analysed. The dominance of cyanobacteria and the presence of bacterial sulfate reducers were confirmed using signature FAs in all three mats. Wax ester analysis suggested the presence of Chloroflexus spp. The dominance of short chain hydrocarbons, wax esters and FAs indicated that microorganisms are the major source of organic matter in these meltwater ponds. A variety of sterols were present in different relative abundances. The greatest diversity of sterols was in Salt Pond, followed by Fresh Pond, which was attributed to differences in the present eukaryotic diversity. Lipid profiles of the three communities were similar despite the presence of a salinity gradient. Analysis of lipid biomarkers allowed the creation of profiles for these unique Antarctic cryo-ecosystems. This will assist in the comparison of present and past microbial communities and in the monitoring of Antarctic biodiversity in response to global climate change and other environmental perturbations.     

The hydromagnesite playas of Atlin, British Columbia, Canada: A biogeochemical model for CO2 sequestration

Anthropogenic greenhouse gas emissions may be offset by sequestering carbon dioxide (CO₂) through the carbonation of magnesium silicate minerals to form magnesium carbonate minerals. The hydromagnesite [Mg₅(CO₃)₄(OH)₂·4H₂O] playas of Atlin, British Columbia, Canada provide a natural model to examine mineral carbonation on a watershed scale. At near surface conditions, CO₂ is biogeochemically sequestered by microorganisms that are involved in weathering of bedrock and precipitation of carbonate minerals. The purpose of this study was to characterize the weathering regime in a groundwater recharge zone and the depositional environments in the playas in the context of a biogeochemical model for CO₂ sequestration with emphasis on microbial processes that accelerate mineral carbonation.Regions with ultramafic bedrock, such as Atlin, represent the best potential sources of feedstocks for mineral carbonation. Elemental compositions of a soil profile show significant depletion of MgO and enrichment of SiO₂ in comparison to underlying ultramafic parent material. Polished serpentinite cubes were placed in the organic horizon of a coniferous forest soil in a groundwater recharge zone for three years. Upon retrieval, the cube surfaces, as seen using scanning electron microscopy, had been colonized by bacteria that were associated with surface pitting. Degradation of organic matter in the soil produced chelating agents and acids that contributed to the chemical weathering of the serpentinite and would be expected to have a similar effect on the magnesium-rich bedrock at Atlin. Stable carbon isotopes of groundwater from a well, situated near a wetland in the southeastern playa, indicate that  12% of the dissolved inorganic carbon has a modern origin from soil CO₂.The mineralogy and isotope geochemistry of the hydromagnesite playas suggest that there are three distinct depositional environments: (1) the wetland, characterized by biologically-aided precipitation of carbonate minerals from waters concentrated by evaporation, (2) isolated wetland sections that lead to the formation of consolidated aragonite sediments, and (3) the emerged grassland environment where evaporation produces mounds of hydromagnesite. Examination of sediments within the southeastern playa–wetland suggests that cyanobacteria, sulphate reducing bacteria, and diatoms aid in producing favourable geochemical conditions for precipitation of carbonate minerals.The Atlin site, as a biogeochemical model, has implications for creating carbon sinks that utilize passive microbial, geochemical and physical processes that aid in mineral carbonation of magnesium silicates. These processes could be exploited for the purposes of CO₂ sequestration by creating conditions similar to those of the Atlin site in environments, artificial or natural, where the precipitation of magnesium carbonates would be suitable. Given the vast quantities of Mg-rich bedrock that exist throughout the world, this study has significant implications for reducing atmospheric CO₂ concentrations and combating global climate change.     

Formation of carbonate concretions in surface sediments of two mud mounds,offshore Costa Rica: a stable isotope study

The surface sediments of two mud mounds (“Mound 11” and “Mound 12”) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO₃). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded δ¹⁸O_carbonate values ranging between 34.0 and 37.7 ‰ Vienna standard mean ocean water (VSMOW) and δ¹³C_carbonate values from ?52.2 to ?14.2 ‰ Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The δ¹⁸O_carbonate values suggest mineral formation from seawater-derived pore fluid (δ¹⁸O_porefluid = 0 ‰ VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (δ¹⁸O_porefluid ≈5 ‰) in Mound 11. A positive correlation between δ¹³C_carbonate and δ¹⁸O_carbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (δ¹³C_porefluid ≈0 ‰) and (2) bicarbonate which formed during the AOM (δ¹³C_porefluid ≈?70 ‰). Furthermore, the δ¹⁸O_porefluid composition, with values up to +4.7 ‰ Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boron-enriched fluids. Earlier, it has been shown that the origin of ¹⁸O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (δ¹³C_CH4 = ?38 ‰). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).     

The calcium carbonate saturation state in cyanobacterial mats throughout Earth’s history

Through early lithification, cyanobacterial mats produced vast amounts of CaCO₃ on Precambrian carbonate platforms (before 540 Myr ago). The superposition of lithified cyanobacterial mats forms internally laminated, macroscopic structures known as stromatolites. Similar structures can be important constituents of Phanerozoic carbonate platforms (540 Myr to present). Early lithification in modern marine cyanobacterial mats is thought to be driven by a metabolically-induced increase of the CaCO₃ saturation state (Ω_CaCO3) in the mat. However, it is uncertain which microbial processes produce the Ω_CaCO3 increase and to which extent similar Ω_CaCO3 shifts were possible in Precambrian oceans whose chemistry differed from that of the modern ocean. I developed a numerical model that calculates Ω_CaCO3 in cyanobacterial mats and used it to tackle these questions. The model is first applied to simulate Ω_CaCO3 in modern calcifying cyanobacterial mats forming at Highborne Cay (Bahamas); it shows that while cyanobacterial photosynthesis increases Ω_CaCO3 considerably, sulphate reduction has a small and opposite effect on mat Ω_CaCO3 because it is coupled to H₂S oxidation with O₂ which produces acidity. Numerical experiments show that the magnitude of the Ω_CaCO3 increase is proportional to DIC in DIC-limited waters (DIC < 3-10 mM), is proportional to pH when ambient water DIC is not limiting and always proportional to the concentration of Ca²⁺ in ambient waters. With oceanic Ca²⁺ concentrations greater than a few millimolar, an appreciable increase in Ω_CaCO3 occurs in mats under a wide range of environmental conditions, including those supposed to exist in the oceans of the past 2.8 Gyr. The likely lithological expression is the formation of the microsparitic stromatolite microtexture—indicative of CaCO₃ precipitation within the mats under the control of microbial activity—which is found in carbonate rocks spanning from the Precambrian to recent. The model highlights the potential for an increase in the magnitude of the Ω_CaCO3 shift in cyanobacterial mats throughout Earth’s history produced by a decrease in salinity and temperature of the ocean, a decrease in atmospheric pCO₂ and an increase in solar irradiance. Such a trend would explain how the formation of the microsparitic stromatolite microtexture was possible as the Ω_CaCO3 of the ocean decreased from the Paleoproterozoic to the Phanerozoic.     

Kurnakovite deposits on the Qinghai-Tibet Plateau (II): an investigation from chemical kinetics of chloropinnoite dissolution

Lakes on the Qinghai-Tibet Plateau (QTP) are of particular interest to researchers because of their unusual high concentrations of lithium (Li), boron (B), and potassium (K). Kurnakovite, a member of the inderite group, is well-distributed on the QTP, however, the geochemical mechanisms of kurnakovite transformation requires further identification and clarification. This study aims to elucidate the geochemical mechanisms of kurnakovite deposits on the QTP from chloropinnoite dissolution using chemical kinetic and spectroscopic techniques. The new borate, chloropinnoite 2MgO · 2B₂O₃ · MgCl₂ · 14H₂O, was obtained from the natural concentrated salt lake brine on the QTP. The kinetics of chloropinnoite dissolved in 4.5 % (wt%) boric acid solution at 303, 313, and 323 K were investigated. The characterization of the phase transitions and the kinetics were carried out by chemical titration analysis, X-ray powder diffraction spectrometry, Fourier Transform Infrared (FT-IR), and Raman spectrometry. The results demonstrate that similar kinetic processes occur at all three temperatures and can be divided into dissolution, supersaturation, and precipitation, according to three distinct kinetic curves. Kurnakovite was the final phase transition (terminal secondary mineral) within the chloropinnoite-boric acid solution. The dissolution rate of chloropinnoite (the dissolution stage) could be described by second order pseudo-homogeneous reaction model. According to the spectroscopy data, geochemical mechanism of kurnakovite was identified. The new geochemical hypothesis well explains the geochemical mechanism of kurnakovite minerals on the QTP.     

东濮凹陷深部次生孔隙成因与储层演化研究

东濮凹陷油气储层埋藏深、总厚度大、次生孔隙发育。据物性剖面和成因研究,由浅至深(1800->5000m)次生储层可划分三带:(1)SA带──表现为有机酸(尤双羧酸)及碳酸对碳酸盐胶结物及骨架长石颗粒的溶蚀;(2)SB带──碳酸对碳酸盐胶结物的溶蚀和异常高压保护;(3)SC带──异常高压保护及无机酸对胶结物的溶蚀。研究表明,高压流体及无机酸(H₂CO₃和H₂S)对东濮凹陷深部储层的形成具有重要意义。     

Experimental and numerical simulation study of the mineral sequestration mechanism of the Shiqianfeng saline aquifers in the Ordos Basin,Northwest China

This study focused on typical injection layers of deep saline aquifers in the Shiqianfeng Formation used in the Carbon Capture and Sequestration Demonstration Projects in the Ordos Basin, Northwest China. The study employed experiments and numerical simulations to investigate the mechanism of CO₂ mineral sequestration in these deep saline aquifers. The experimental results showed that the dissolved minerals are plagioclase, hematite, illite–smectite mixed layer clay and illite, whereas the precipitated minerals are quartz (at 55, and 70 °C) and kaolinite (at 70 °C). There are rare carbonate mineral precipitations at the experimental time scale, while the precipitation of quartz as a product of the dissolution of silicate minerals and some intermediate minerals rich in K and Mg that transform to clay minerals, reveals the possibility of carbonate precipitation at the longer time scale. These results are consistent with some results previously reported in the literature. We calibrated the kinetic parameters of mineral dissolution and precipitation by these experimental results and then simulated the CO₂ mineral sequestration under deep saline aquifer conditions. The simulation results showed that the dissolved minerals are albite, anorthite and minor hematite, whereas the precipitated minerals are calcite, kaolinite and smectite at 55 and 70 °C. The geochemical reaction of illite is more complex. At 55 °C, illite is dissolved at the relatively lag time and transformed to dawsonite; at 70 °C, illite is precipitated in the early reaction period and then transformed to kaolinite. Based on this research, sequestrated CO₂ minerals, which are mainly related to the temperature of deep saline aquifers in Shiqianfeng Fm., are calcite and dawsonite at lower temperature, and calcite at higher temperature. The simulation results also establish that calcite could precipitate over a time scale of thousands of years, and the higher the temperature the sooner such a process would occur due to increased reaction rates. These characteristics are conducive, not only to the earlier occurrence of mineral sequestration, but also increase the sequestration capacity of the same mineral components. For a sequestration period of 10,000 years, we determined that the mineral sequestration capacity is 0.786 kg/m³ at 55 °C, and 2.180 kg/m³ at 70 °C. Furthermore, the occurrence of mineral sequestration indirectly increases the solubility of CO₂ in the early reaction period, but this decreases with the increase in temperature.