Precipitate Carbonate Minerals Research Articles

An integrated experimental-modeling approach to identify key processes for carbon mineralization in fractured mafic and ultramafic rocks.

Controlling atmospheric warming requires immediate reduction of carbon dioxide (CO2) emissions, as well as the active removal and sequestration of CO2 from current point sources. One promising proposed strategy to reduce atmospheric CO2 levels is geologic carbon sequestration (GCS), where CO2 is injected into the subsurface and reacts with the formation to precipitate carbonate minerals. Rapid mineralization has recently been reported for field tests in mafic and ultramafic rocks. However, unlike saline aquifers and depleted oil and gas reservoirs historically considered for GCS, these formations can have extremely low porosities and permeabilities, limiting storage volumes and reactive mineral surfaces to the preexisting fracture network. As a result, coupling between geochemical interactions and the fracture network evolution is a critical component of long-term, sustainable carbon storage. In this paper, we summarize recent advances in integrating experimental and modeling approaches to determine the first-order processes for carbon mineralization in a fractured mafic/ultramafic rock system. We observe the critical role of fracture aperture, flow, and surface characteristics in controlling the quantity, identity, and morphology of secondary precipitates and present where the influence of these factors can be reflected in newly developed thermo-hydro-mechanical-chemical models. Our findings provide a roadmap for future work on carbon mineralization, as we present the most important system components and key challenges that we are overcoming to enable GCS in mafic and ultramafic rocks.

Characterizing Microbial and CO2-Induced Carbonate Minerals: Implications for Soil Stabilization in Sandy Environments

This study aimed to investigate the structure and shape of carbonate crystals induced through microbial activity and carbon dioxide reactions in the sand. The strength of sandy soil treated with carbonate minerals was subsequently determined using unconfined compression strength (UCS) tests. Sporoscarcina pasteurii bacteria were used to produce an aqueous solution of free carbonate ions (CO32−) under laboratory circumstances called microbial-induced carbonate precipitation (MICP). In CO2-induced carbonate precipitation (CICP), carbon dioxide was added to a sodium hydroxide solution to form free carbonate ions (CO32−). Different carbonate mineral compositions were then provided by adding Fe2+, Mg2+, and Ca2+ ions to carbonate ions (CO32−). In the MICP and CICP procedures, the results of scanning electron microscopy (SEM) and X-ray powder diffraction (XRD) revealed a distinct morphology of any type of carbonate minerals. Vaterite (CaCO3), siderite (FeCO3), nesquehonite (MgCO3(H2O)3), and dolomite (CaMg(CO3)2 were produced in MICP. Calcite (CaCO3), siderite (FeCO3), nesquehonite (MgCO3(H2O)3), and high-Mg calcite (Ca-Mg(CO3)) were produced in CICP. According to UCS data, siderite and high-Mg calcite/dolomite had more effectiveness in increasing soil strength (63–72 kPa). The soils treated with nesquehonite had the lowest strength value (25–29 kPa). Mineral-treated soils in CICP showed a slightly higher UCS strength than MICP, which could be attributable to greater particle size and interlocking. This research focused on studying the mineralogical properties of precipitated carbonate minerals by CICP and MICP methods to suggest a promising environmental method for soil reinforcement.

Assessment the ability of water with different ionic strength to dissolve and precipitate carbonate minerals according to omega(Ω) and saturation index (SI)

The study included five locations in Kurdistan Region, Iraq, represented by the soils of Zawita, Zakho, Dukan, Smaquli and Aqrah, in order to know the solubility and precipitation of carbonate minerals based on the values of omega (Ω) and saturation index (SI) using water of different ionic strength (chloride water, sulfur water, Tigris river water).the results showed that the dolomite mineral was more precipitated in term of omega (9.38 * 108) and the saturation index (8.97) in the case of chloride water, while magnesite was soluble where the value of omega was)0.01) and saturation index (-1.85), then when using sulfur water the same behavior appeared for the same mineral (dolomite) in term of precipitation (SI = 9.08) and magnesite in term of solubility (SI = -0.94). The same applies to the water of the Tigris River. As a general conclusion, the dolomite was more precipitated and the magnesite was more soluble in the presence of chloride water compared with the water of the Tigris River and the sulfur water.

The temporal evolution of the carbon isotope composition of calcite in the presence of cyanobacteria

Quantifying the link between cyanobacterial activity and the carbon isotope signature of precipitated carbonate minerals is crucial for reconstructing the environmental conditions present at the time of carbonate mineral formation. In this study, calcite was precipitated in the presence and absence of Synechococcus sp. cyanobacteria in batch reactors. The temporal evolution of the carbon isotope composition of calcite (δ13CCalcite) and dissolved inorganic carbon (δ13CDIC) was monitored to evaluate the rate and degree to which the carbon isotope compositions in calcite are modified during and after its precipitation. The presence of cyanobacteria promoted calcium carbonate formation by increasing fluid pH and the CaCO3 saturation state. It also changed significantly the carbon isotope composition of dissolved inorganic carbon due to the preferential incorporation of 12C into the biomass. This generated an isotope disequilibrium between the calcite and the aqueous fluid phase over time after the calcite precipitated. The carbon isotope composition of the calcite evolved continuously towards mineral-fluid isotope equilibrium after its precipitation, at geometric surface area normalized rates ranging from 1.75 × 10−14 to 1.71 × 10−13 mol 13C/m2/s. These rates are sufficiently fast such that the δ13CDIC value of aqueous fluids in calcite-rich rocks would be buffered by the δ13CCalcite value of the co-existing calcite. Mass balance calculations suggest that the carbon isotope composition of calcite could change noticeably when the calcite is in isotope disequilibrium with its co-existing fluid, for example through the presence of a local 12C sink such as photosynthetic microorganisms or 12C source such as decomposition of organic material.

Field detection of urease and carbonic anhydrase activity using rapid and economical tests to assess microbially induced carbonate precipitation.

Microbial precipitation of calcium carbonate is a widespread environmental phenomenon that has diverse engineering applications, from building and soil restoration to carbon sequestration. Urease-mediated ureolysis and CO2 (de)hydration by carbonic anhydrase (CA) are known for their potential to precipitate carbonate minerals, yet many environmental microbial community studies rely on marker gene or metagenomic approaches that are unable to determine in situ activity. Here, we developed fast and cost-effective tests for the field detection of urease and CA activity using pH-sensitive strips inside microcentrifuge tubes that change colour in response to the reaction products of urease (NH3 ) and CA (CO2 ). The urease assay proved sensitive and useful in the field to detect in situ activity in biofilms from a saline lake, a series of calcareous fens, and ferrous springs, finding relatively high urease activity in lake samples. Incubations of lake microbes with urea resulted in significantly higher CaCO3 precipitation compared to incubations with a urease inhibitor, showing that the rapid assay indicated an on-site active metabolism potentially mediating carbonate precipitation. The CA assay, however, showed less sensitivity compared to the urease test. While its sensitivity limits its utility, the assay may still be useful as a preliminary indicator given the paucity of other means for detecting CA activity in the field. Field urease, and potentially CA, activity assays complement molecular approaches and facilitate the search for carbonate-precipitating microbes and their in situ activity, which could be applied toward agriculture, engineering and carbon sequestration technologies.

Bio-Precipitation of Carbonate and Phosphate Minerals Induced by the Bacterium Citrobacter freundii ZW123 in an Anaerobic Environment

In this study, a facultative anaerobic strain isolated from marine sediments and identified as Citrobacter freundii, was used to induce the precipitation of carbonate and phosphate minerals in the laboratory under anaerobic conditions. This is the first time that the ability of C. freundii ZW123 to precipitate carbonate and phosphate minerals has been demonstrated. During the experiments, carbonic anhydrase, alkaline phosphatase and ammonium released by the bacteria not only promoted an increase in pH, but also drove the supersaturation and precipitation of carbonate and phosphate minerals. The predominant bio-mediated minerals precipitated at various Mg/Ca molar ratios were calcite, vaterite, Mg-rich calcite, monohydrocalcite and struvite. A preferred orientation towards struvite was observed. Scanning transmission electron microscopy (STEM) and elemental mapping showed the distribution of magnesium and calcium elements within Mg-rich calcite. Many organic functional groups, including C=O, C–O–C and C–O, were detected within the biominerals, and these functional groups were also identified in the associated extracellular polymeric substances (EPS). Fifteen kinds of amino acid were detected in the biotic minerals, almost identical to those of the EPS, indicating a close relationship between EPS and biominerals. Most amino acids are negatively charged and able to adsorb cations, providing an oversaturated microenvironment to facilitate mineral nucleation. The X-ray photoelectron spectroscopy (XPS) spectrum of struvite shows the presence of organic functional groups on the mineral surface, suggesting a role of the microorganism in struvite precipitation. The ZW123 bacteria provided carbon and nitrogen for the formation of the biotic minerals through their metabolism, which further emphasizes the close relationship between biominerals and the microorganisms. Thermal studies showed the enhanced thermal stability of biotic minerals, perhaps due to the participation of the bacteria ZW123. The presence of amino acids such as Asp and Glu may explain the high magnesium content of some calcites. Molecular dynamics simulations demonstrated that the morphological change and preferred orientation were likely caused by selective adsorption of EPS onto the various struvite crystal surfaces. Thus, this study shows the significant role played by C. freundii ZW123 in the bioprecipitation of carbonate and phosphate minerals and provides some insights into the processes involved.

Fate of transition metals during passive carbonation of ultramafic mine tailings via air capture with potential for metal resource recovery

Mineral carbonation in ultramafic mine tailings is generally accepted to be a safe and long term means of trapping and storing CO2 within the structures of minerals, but it poses the risk of releasing potentially hazardous metal contaminants from mineral wastes into the environment. Stockpiles of reactive, finely pulverised ultramafic mine tailings are ideal natural laboratories for the observation and promotion of the carbonation of Mg-silicate and Mg-hydroxide waste minerals via reaction with atmospheric or industrial CO2. However, ultramafic mine tailings commonly contain first-row transition metals (e.g., Cr, Co, Cu, Ni) in potentially toxic concentrations within the crystal structures of Mg-silicates, sulphides, and oxides. These transition metals are likely to be mobilised by mineral carbonation reactions, which require mineral dissolution to supply cations for reaction with carbon. At Woodsreef Chrysotile Mine, New South Wales, Australia, transition metals (i.e., Fe, Cr, Ni, Mn, Co, Cu) are most concentrated within minor oxides (magnetite and chromite) and trace alloys (awaruite, Ni2-3Fe and wairauite, CoFe) in serpentine tailings, however, mobilisation of transition metals appears to occur predominantly during dissolution of serpentine and brucite, which are more abundant and reactive phases, respectively. Here, we present new synchrotron X-ray fluorescence mapping data that provide insights into the mobility of first-row transition metals (Fe, Cr, Ni, Mn, Co, Cu) during weathering and carbonation of ultramafic mine tailings collected from the Woodsreef Chrysotile Mine. These data indicate that the recently precipitated carbonate minerals, hydromagnesite [Mg5(CO3)4(OH)2·4H2O] and pyroaurite [Mg6Fe2(CO3)(OH)16·4H2O] sequester trace metals from the tailings at concentrations of 10 s–100 s of ppm, most likely via substitution for Mg or Fe within their crystal structures, or by the physical trapping of small (μm-scale) transition-metal-rich grains (i.e., magnetite, chromite, awaruite), which are stabilised within alkaline carbonate cements. Trace transition metals are present at relatively high concentrations in the bulk tailings (i.e., ∼0.3 wt.% NiO and Cr2O3) and they are largely retained within the unaltered mineral assemblage. The weathering products that occur at the surface of the tailings and form a cement between grains of partially dissolved gangue minerals immobilise transition metals on spatial scales of micrometres and at comparable concentrations to those observed in the unaltered tailings. The end result is that trace metals are not present at detectable levels within mine pit waters. Our observations of metal mobility during passive carbonation suggest that mineral products of accelerated carbonation treatments are likely to sequester trace metals. Thus, accelerated carbonation is unlikely to pose an environmental risk in the form of metalliferous drainage so long as the neutralisation potential of the tailings is not exceeded.Understanding both trace transition metal geochemistry and mineralogy within materials targeted for mineral carbonation could allow optimisation of treatment processes and design for recovery of valuable metals. In ex situ reactors employing acid pre-treatments, trace metals mobilised from reactive phases such as serpentine and brucite could potentially be recovered using pH-swing methods, while recalcitrant metal-rich accessory minerals, including magnetite, awaruite and chromite, could be recovered from treated residue material by conventional mineral separation processes. Recovery of valuable metals (i.e., Ni, Cr and Co) as by-products of accelerated mineral carbonation technologies could also provide an important economic incentive to support broader adoption of this technology.

The role of microbial iron reduction in the formation of Proterozoic molar tooth structures

Molar tooth structures are poorly understood early diagenetic, microspar-filled voids in clay-rich carbonate sediments. They are a common structure in sedimentary successions dating from 2600–720 Ma, but do not occur in rocks older or younger, with the exception of two isolated Ediacaran occurrences. Despite being locally volumetrically significant in carbonate rocks of this age, their formation and disappearance in the geological record remain enigmatic. Here we present iron isotope data, supported by carbon and oxygen isotopes, major and minor element concentrations, and total organic carbon and sulphur contents for 87 samples from units in ten different basins spanning ca. 1900–635 Ma. The iron isotope composition of molar tooth structures is almost always lighter (modal depletion of 2‰) than the carbonate or residue components in the host sediment. We interpret the isotopically light iron in molar tooth structures to have been produced by dissimilatory iron reduction utilising Fe-rich smectites and Fe-oxyhydroxides in the upper sediment column. The microbial conversion of smectite to illite results in a volume reduction of clay minerals (∼30%) while simultaneously increasing pore water alkalinity. When coupled with wave loading, this biogeochemical process is a viable mechanism to produce voids and subsequently precipitate carbonate minerals. The disappearance of molar tooth structures in the mid-Neoproterozoic is likely linked to a combination of a decrease in smectite abundance, a decline in the marine DIC reservoir, and an increase in the concentration of O2 in shallow seawater.

Impact of elevated CO2 concentrations on carbonate mineral precipitation ability of sulfate-reducing bacteria and implications for CO2 sequestration

Interest in anthropogenic CO2 release and associated global climatic change has prompted numerous laboratory-scale and commercial efforts focused on capturing, sequestering or utilizing CO2 in the subsurface. Known carbonate mineral precipitating microorganisms, such as the anaerobic sulfate-reducing bacteria (SRB), could enhance the rate of conversion of CO2 into solid minerals and thereby improve long-term storage of captured gasses. The ability of SRB to induce carbonate mineral precipitation, when exposed to atmospheric and elevated pCO2, was investigated in laboratory scale tests with bacteria from organic-rich sediments collected from hypersaline Lake Estancia, New Mexico. The enriched SRB culture was inoculated in continuous gas flow and batch reactors under variable headspace pCO2 (0.0059 psi to 20 psi). Solution pH, redox conditions, sulfide, calcium and magnesium concentrations were monitored in the reactors. Those reactors containing SRB that were exposed to pCO2 of 14.7 psi or less showed Mg-calcite precipitation. Reactors exposed to 20 psi pCO2 did not exhibit any carbonate mineralization, likely due to the inhibition of bacterial metabolism caused by the high levels of CO2. Hydrogen, lactate and formate served as suitable electron donors for the SRB metabolism and related carbonate mineralization. Carbon isotopic studies confirmed that ∼53% of carbon in the precipitated carbonate minerals was derived from the CO2 headspace, with the remaining carbon being derived from the organic electron donors, and the bicarbonate ions available in the liquid medium. The ability of halotolerant SRB to induce the precipitation of carbonate minerals can potentially be applied to the long-term storage of anthropogenic CO2 in saline aquifers and other ideal subsurface rock units by converting the gas into solid immobile phases.

Microbialite response to an anthropogenic salinity gradient in Great Salt Lake, Utah.

A railroad causeway across Great Salt Lake, Utah (GSL), has restricted water flow since its construction in 1959, resulting in a more saline North Arm (NA; 24%-31% salinity) and a less saline South Arm (SA; 11%-14% salinity). Here, we characterized microbial carbonates collected from the SA and the NA to evaluate the effect of increased salinity on community composition and abundance and to determine whether the communities present in the NA are still actively precipitating carbonate or if they are remnant features from prior to causeway construction. SSU rRNA gene abundances associated with the NA microbialite were three orders of magnitude lower than those associated with the SA microbialite, indicating that the latter community is more productive. SSU rRNA gene sequencing and functional gene microarray analyses indicated that SA and NA microbialite communities are distinct. In particular, abundant sequences affiliated with photoautotrophic taxa including cyanobacteria and diatoms that may drive carbonate precipitation and thus still actively form microbialites were identified in the SA microbialite; sequences affiliated with photoautotrophic taxa were in low abundance in the NA microbialite. SA and NA microbialites comprise smooth prismatic aragonite crystals. However, the SA microbialite also contained micritic aragonite, which can be formed as a result of biological activity. Collectively, these observations suggest that NA microbialites are likely to be remnant features from prior to causeway construction and indicate a strong decrease in the ability of NA microbialite communities to actively precipitate carbonate minerals. Moreover, the results suggest a role for cyanobacteria and diatoms in carbonate precipitation and microbialite formation in the SA of GSL.

Biomineralization of Carbonate by Terrabacter Tumescens for Heavy Metal Removal and Biogrouting Applications

AbstractThe ability of Terrabacter tumescens to precipitate carbonate minerals has been demonstrated for the first time. Biomineralization of nickel, copper, lead, cobalt, zinc, cadmium and calcium by T. tumescens and mineral precipitations in both liquid and porous media were investigated. T. tumescens produced the enzyme urease which can hydrolyze urea. Due to this enzymatic reaction, soil pH increased and carbonate was produced, which results in mineralization of the soluble heavy metal ions present in soil water and their ultimate conversion to carbonates. And we studied the process of calcium carbonate precipitation induced by T. tumescens in sand column. The precipitated minerals were studied by scanning electron microscopy and X-ray diffraction, bioaccumulated divalent metal cation were deposited around the cell envelope as rhombohedral, sphere and needle shaped crystalline carbonate compounds. T. tumescens can play important role in heavy metal bioremediation and increase the strength and stiffnes...

Fluid environment for preservation of pore spaces in a deep dolomite reservoir

AbstractWell TS1 reveals many uncemented pores and vugs at depths of more than 8000 m in a deep Cambrian dolomite reservoir in the Tarim Basin, northwestern China. The fluid environment and mechanism required for the preservation of reservoir spaces have yet not been well constrained. Carbon, oxygen, and strontium isotope compositions and fluid inclusion data suggest two types of fluids, meteoric water and hydrothermal fluid, affecting the Lower Paleozoic carbonate reservoirs in the Tarim Basin. Based on simulation using a thermodynamic model for H2O‐CO2‐NaCl‐CaCO3 system, meteoric water has the ability to continuously dissolve carbonate minerals during downward migration from the surface to deep strata until it reaches a transition depth, below which it will begin to precipitate carbonate minerals to fill preexisting pore spaces. In contrast, hydrothermal fluid has the ability to dissolve carbonate in deep strata and precipitate carbonate in shallow strata during upward migration. Based on the dissolution–precipitation characteristics of the two types of fluids, the ideal fluid environment for the preservation of preexisting reservoir spaces occurs when carbonate reservoir is neither in the CaCO3 precipitation domain of meteoric water nor in the CaCO3 precipitation domain of hydrothermal fluid. Taking the Lower Paleozoic carbonate reservoirs in the north uplift area as an example, the spaces in the deep Cambrian dolomite reservoir near well TS1 were seldom filled because thick Ordovician deposits blocked meteoric water from migrating downward into the Cambrian dolomite reservoir and because the Cambrian dolomite reservoir has been in the domain of hydrothermal dissolution since the Permian. The deep carbonate layers in basins elsewhere with a similar fluid environment may have high uncemented porosity and consequently have good hydrocarbon exploration potential.

Characterization of mechanisms and processes of groundwater salinization in irrigated coastal area using statistics, GIS, and hydrogeochemical investigations.

Coastal aquifers are at threat of salinization in most parts of the world. This study was carried out in coastal shallow aquifers of Aousja-Ghar El Melh and Kalâat el Andalous, northeastern of Tunisia with an objective to identify sources and processes of groundwater salinization. Groundwater samples were collected from 42 shallow dug wells during July and September 2007. Chemical parameters such as Na(+), Ca(2+), Mg(2+), K(+), Cl(-), SO4 (2-), HCO3 (-), NO3 (-), Br(-), and F(-) were analyzed. The combination of hydrogeochemical, statistical, and GIS approaches was used to understand and to identify the main sources of salinization and contamination of these shallow coastal aquifers as follows: (i) water-rock interaction, (ii) evapotranspiration, (iii) saltwater is started to intrude before 1972 and it is still intruding continuously, (iv) irrigation return flow, (v) sea aerosol spray, and finally, (vi) agricultural fertilizers. During 2005/2006, the overexploitation of the renewable water resources of aquifers caused saline water intrusion. In 2007, the freshening of a brackish-saline groundwater occurred under natural recharge conditions by Ca-HCO3 meteoric freshwater. The cationic exchange processes are occurred at fresh-saline interfaces of mixtures along the hydraulic gradient. The sulfate reduction process and the neo-formation of clays minerals characterize the hypersaline coastal Sebkha environments. Evaporation tends to increase the concentrations of solutes in groundwater from the recharge areas to the discharge areas and leads to precipitate carbonate and sulfate minerals.

Geochemical processes, evidence and thermodynamic behavior of dissolved and precipitated carbonate minerals in a modern seawater/freshwater mixing zone of a small tropical island

The geochemical processes and thermodynamic behavior of dissolved and precipitated carbonate minerals controlling the hydrochemistry of an aquifer in the seawater/freshwater mixing zone of a small island are identified. Field and laboratory analyses, geochemical modeling (PHREEQC) and multivariate statistical analysis (MSA) provide a quantitative interpretation for the geochemistry of the carbonate-dominated aquifer. Geochemical analyses and modeling results show that dissolution and re-precipitation of CaCO3 are the prevalent processes governing geochemical reactions in the mixing zone. Furthermore, this was confirmed by coherent statistical output that incorporates Principle Component Analysis (PCA) and k-means Cluster Analysis (k-CA). Generally, the composition of the lowland sandy soil was rather homogeneous and was primarily composed of quartz, aragonite, calcite and Mg-calcite. Thermodynamic model calculations indicate that the carbonate minerals calcite, aragonite and dolomite are supersaturated in the mixing zone. Nevertheless, Powder X-ray Diffraction (PXRD) and Scanning Electron Microscope (SEM) examination verified the occurrence of low-Mg-calcite (LMC) and the absence of dolomite, attributed to thermodynamic/kinetic hindrance, cation disorder and the presence of dolomite crystal growth rate inhibitors (such as SO4). The results suggest that dissolution of aragonite and precipitation of LMC drives the solid phase geochemistry in the small tropical island aquifer.

Precipitation of Carbonates and Phosphates by Bacteria in Extract Solutions from a Semi-arid Saline Soil. Influence of Ca2+ and Mg2+Concentrations and Mg2+/Ca2+ Molar Ratio in Biomineralization

We examine the ability of bacteria from a saline soil (Arenic-Gypsic-Hyposalic Solonchak) from the Santa-Pola marine saltern (Alicante, Spain) to precipitate carbonate and phosphate minerals. Solid culture media were prepared from natural soil extracts, from natural soil extracts amended with organic material in different proportions, and by modifying the Ca 2+ and Mg 2+ concentrations and the Mg 2+ /Ca 2 + molar ratio. A high percentage of moderately halophilic bacteria were able to form biominerals (calcite, magnesian calcite and/or struvite) in natural soil extracts with small amounts of added organic material and in ionically modified natural soil extracts. Light microscopy revealed three different types of bio-mineralization: colonies that precipitate carbonates, colonies that precipitate struvite, and colonies that precipitate both types of minerals. The precipitation of carbonates and struvite is not simultaneous, but successive. The concentration of Ca 2+ and the Mg 2+ /Ca 2 + molar ratio were more influential than the absolute amount of Mg 2+ on the precipitation of minerals. The higher the calcium concentrations are, the more carbonate-forming colonies there are and the fewer struvite-forming colonies. The bioliths precipitated were analyzed by Powder X-Ray Diffraction (PXRD) and Scanning Electron Microscope (SEM). In the magnesian calcites precipitated (Ca 1 − n Mg n CO 3 ), “n” (amount of magnesium that replaces calcium by formula) varied from 0.058 to 0.342. Struvite crystals are polyhedral and around 500 μm, while carbonate crystals are smaller (< 100 μm), spherical and usually in aggregates. The precipitation of minerals studied shows an active role of the bacteria, but the geochemical conditions are clearly influential. It may therefore be considered “induced biomineralization.” The results point out the possibility that in some soils the C, N, P, Ca and Mg cycles are coupled due to bacterial biomineralization.

Carbonate and Phosphate Precipitation by Chromohalobacter marismortui

The ability of Chromohalobacter marismortui to precipitate carbonate and phosphate minerals has been demonstrated for the first time. Mineral precipitation in both solid and liquid media at different salts concentrations and different magnesium/calcium ratios occurred whereas crystal formation was not observed in the control. The precipitated minerals were studied by X-ray diffraction, scanning electron microscopy and EDX, and were different in liquid and solid media. In liquid media aragonite, struvite, vaterite and monohydrocalcite were precipitated forming crystals and bioliths. Bioliths accreted preferentially close to organic pellicles, whereas struvite preferentially grows in microenvironments free of such pellicles. Magnesian calcite, calcian-magnesian kutnahorite, “proto-dolomite” and huntite were formed in solid media. The Mg content of the magnesian calcite and of Ca-Mg kutnahorite also varied depending on the salt concentration of the culture media. This is the first report on bacterial precipitation of Ca-Mg kutnahorite and huntite in laboratory cultures. The results of this research show the active role played by C. marismortui in mineral precipitation, and allow us to compare them with those obtained previously using other taxonomic groups of moderately halophilic bacteria.

Carbonate and Phosphate Precipitation by Chromohalobacter marismortui

The ability of Chromohalobacter marismortui to precipitate carbonate and phosphate minerals has been demonstrated for the first time. Mineral precipitation in both solid and liquid media at different salts concentrations and different magnesium/calcium ratios occurred whereas crystal formation was not observed in the control. The precipitated minerals were studied by X-ray diffraction, scanning electron microscopy and EDX, and were different in liquid and solid media. In liquid media aragonite, struvite, vaterite and monohydrocalcite were precipitated forming crystals and bioliths. Bioliths accreted preferentially close to organic pellicles, whereas struvite preferentially grows in microenvironments free of such pellicles. Magnesian calcite, calcian-magnesian kutnahorite, “proto-dolomite” and huntite were formed in solid media. The Mg content of the magnesian calcite and of Ca-Mg kutnahorite also varied depending on the salt concentration of the culture media. This is the first report on bacterial precipitation of Ca-Mg kutnahorite and huntite in laboratory cultures. The results of this research show the active role played by C. marismortui in mineral precipitation, and allow us to compare them with those obtained previously using other taxonomic groups of moderately halophilic bacteria.

Geochemical monitoring of fluid-rock interaction and CO 2 storage at the Weyburn CO 2-injection enhanced oil recovery site, Saskatchewan, Canada

The Weyburn Oil Field, Saskatchewan is the site of a large (5000 tonnes/day of CO 2) CO 2-EOR injection project By EnCana Corporation. Pre- and post-injection samples (Baseline and Monitor-1, respectively) of produced fluids from approximately 45 vertical wells were taken and chemically analyzed to determine changes in the fluid chemistry and isotope composition between August 2000 and March 2001. After 6 months of CO 2 injection, geochemical parameters including pH, [HCO 3], [Ca], [Mg], and δ 13CO 2(g) point to areas in which injected CO 2 dissolution and reservoir carbonate mineral dissolution have occurred. Pre-injection fluid compositions suggest that the reservoir brine in the injection area may be capable of storing as much as 100 million tonnes of dissolved CO 2. Modeling of water-rock reactions show that clay minerals and feldspar, although volumetrically insignificant, may be capable of acting as pH buffers, allowing injected CO 2 to be stored as bicarbonate in the formation water or as newly precipitated carbonate minerals, given favorable reaction kinetics.

Irrigation Increases Inorganic Carbon in Agricultural Soils

Inorganic C reactions are among the most important chemical reactions that occur in irrigated soils and may contribute to the total amount of C sequestered in those soils. Because CO2 can escape from soils to the atmosphere or return to precipitate carbonate minerals, soils are open systems with regard to inorganic C. We measured inorganic and organic C stored in southern Idaho soils having long-term land-use histories that supported native sagebrush vegetation (NSB), irrigated moldboard plowed crops (IMP), irrigated conservation (chisel) tilled crops (ICT), and irrigated pasture systems (IP). Inorganic C and total C (inorganic + organic C) in soil decreased in the order IMP>ICT>IP>NSB. We use our findings to estimate that amount of possible inorganic and total C sequestration if irrigated agriculture were expanded by 10%. If irrigated agricultural land were expanded by 10% worldwide and NSB were converted to IMP, a possible 1.60 × 109 Mg inorganic C (2.78% of the total C emitted in the next 30 years) could be sequestered in soil. If irrigated agricultural land were expanded by 10% worldwide and NSB were converted to ICT, a possible 1.10 × 109 Mg inorganic C (1.87% of the total C emitted in the next 30 years) could be sequestered in soil. If irrigated agricultural land were expanded worldwide and NSB were converted to IP, a possible gain of 2.6 × 108 Mg inorganic C (0.04% of the total C emitted in the next 30 years) could be sequestered in soils. Inorganic C sequestered from land-use changes have little potential to make a significant impact on the concentration of atmospheric CO2. However, when coupled with organic C and altering land use to produce crops on high-output irrigated agriculture while selected less productive rain-fed agricultural land was returned to temperate forest or native grassland, there could be reductions in atmospheric CO2.

Speciation of elements in lake sediments investigated using x-ray fluorescence and inductively coupled plasma atomic emission spectrometry

Radioisotope-excited energy-dispersive x-ray fluorescence (EDXRF) analysis and inductively coupled plasma atomic emission spectrometry (ICP-AES) were used to investigate the speciation of elements in sediment samples collected from a peat bog in Hungary. Lake and bog sediments are a mixture of allogenic material (clastic mineral particles resulting from erosion of the catchment soils or from dust) and authigenic components (deposited directly from aquatic solution through biological uptake or chemical sorption, biochemically precipitated carbonate minerals, Fe and Mn oxides, oxyhydroxides, sulphides, sulphates, phosphates, etc.). After removing the authigenic fraction by wet digestion, element concentrations in the acid insoluble residue were determined by XRF and those in the authigenic part by ICP-AES. On the basis of chemical composition, the sediment sequence was divided into three zones reflecting different environmental regimes during sediment accumulation. Allogenic and authigenic species of elements provided relevant information on environmental processes which changed the soil and vegetation in NE Hungary during the early postglacial. © 1988 John Wiley & Sons, Ltd.