Metal release from dolomites at high partial-pressures of CO2

The potential for metal release associated with CO₂ leakage from underground storage formations into shallow aquifers is an important consideration in assessment of risk associated with CO₂ sequestration. Metal release can be driven by acidification of groundwaters caused by dissolution of CO₂ and subsequent dissociation of carbonic acid. Thus, acidity is considered one of the main drivers for water quality degradation when evaluating potential impacts of CO₂ leakage. Dissolution of carbonate minerals buffers the increased acidity. Thus, it is generally thought that carbonate aquifers will be less impacted by CO₂ leakage than non-carbonate aquifers due to their high buffering potential. However, dissolution of carbonate minerals can also release trace metals, often present as impurities in the carbonate crystal structure, into solution. The impact of the release of trace metals through this mechanism on water quality remains relatively unknown. In a previous study we demonstrated that calcite dissolution contributed more metal release into solution than sulfide dissolution or desorption when limestone samples were dissolved in elevated CO₂ conditions. The study presented in this paper expanded our work to dolomite formations and details a thorough investigation on the role of mineral composition and mechanisms on trace element release in the presence of CO₂. Detailed characterization of samples from dolomite formations demonstrated stronger associations of metal releases with dissolution of carbonate mineral phases relative to sulfide minerals or surface sorption sites. Aqueous concentrations of Sr²⁺, CO²⁺, Mn²⁺, Ni²⁺, Tl⁺, and Zn²⁺ increased when these dolomite rocks were exposed to elevated concentrations of CO₂. The aqueous concentrations of these metals correlate to aqueous concentrations of Ca²⁺ throughout the experiments. All of the experimental evidence points to carbonate minerals as the dominant source of metals from these dolomite rocks to solution under experimental CO₂ leakage conditions. Aqueous concentrations of Ca²⁺ and Mg²⁺ predicted from numerical simulation of kinetic dolomite dissolution match those observed in the experiments when the surface area is three to five orders of magnitude lower than the surface area of the samples measured by gas adsorption.     

Formation of lacustrine dolomite in the late Miocene marginal lakes of the East Mediterranean (Northern Israel)

The study focuses on the formation of lacustrine dolomite in late Miocene lakes, located at the East Mediterranean margins (Northern Israel). These lakes deposited the sediments of the Bira (Tortonian) and Gesher (Messinian) formations that comprise sequences of dolostone and limestone. Dolostones are bedded, consist of small‐sized (<7 μm), Ca‐rich (52 to 56 mol %) crystals with relatively low ordering degrees, and present evidence for replacement of CaCO₃ components. Limestones are comprised of a wackestone to mudstone matrix, freshwater macrofossils and intraclasts (mainly in the Bira Formation). Sodium concentrations and isotope compositions differ between limestones and dolostones: Na = ~100 to 150 ppm; ~1000 to 2000 ppm; δ¹⁸O = ?3·8 to ?1·6‰; ?2·0 to +4·3‰; δ¹³C = ?9·0 to ?3·4‰; ?7·8 to 0‰ (VPDB), respectively. These results indicate a climate‐related sedimentation during the Tortonian and early Messinian. Wet conditions and positive freshwater inflow into the carbonate lake led to calcite precipitation due to intense phytoplankton blooms (limestone formation). Dry conditions and enhanced evaporation led to precipitation of evaporitic CaCO₃ in a terminal lake, which caused an increased Mg/Ca ratio in the residual waters and penecontemporaneous dolomitization (dolostone formation). The alternating lithofacies pattern reveals eleven short‐term wet–dry climate‐cycles during the Tortonian and early Messinian. A shift in the environmental conditions under which dolomite formed is indicated by a temporal decrease in δ¹⁸O of dolostones and Na content of dolomite crystals. These variations point to decreasing evaporation degrees and/or an increased mixing with meteoric waters towards the late Messinian. A temporal decrease in δ¹³C of dolostones and limestones and appearance of microbial structures in close association with dolomite suggest that microbial activity had an important role in allowing dolomite formation during the Messinian. Microbial mediation was apparently the main process that enabled local growth of dolomite under wet conditions during the latest Messinian.     

Dolomite Versus Calcite Weathering in Hydrogeochemically Diverse Watersheds Established on Bedded Carbonates (Sava and So?a Rivers, Slovenia)

The relative contributions of dolomite to calcite weathering related to riverine fluxes are investigated on a highly resolved spatial scale in the diverse watersheds of Slovenia, which previous work has shown have some of the highest carbonate-weathering intensities in the world and suggests that dolomite weathering is favored over limestone weathering in mixed carbonate watersheds. The forested Sava and So?a River watersheds of Slovenia with their headwaters in the Julian Alps drain alpine regions with thin soils (<30 cm) and dinaric karst regions with thicker soils (0 to greater than 70 cm) all developed over bedded Mesozoic carbonates (limestone and dolomite), and siliclastic sediments is the ideal location for examining temperate zone carbonate weathering. This study extends previous work, presenting geochemical data on source springs and documenting downstream geochemical fluctuations within tributaries of the Sava and So?a Rivers. More refined sampling strategies of springs and discrete drainages permit directly linking the stream Mg²⁺/Ca²⁺ ratios to the local bedrock lithology and the HCO₃ ^? concentrations to the relative soil depths of the tributary drainages. Due to differences in carbonate source lithologies of springs and tributary streams, calcite and dolomite weathering end members can be identified. The Mg²⁺/Ca²⁺ ratio of the main channel of the Sava River indicates that the HCO₃ ^? concentration can be attributed to nearly equal proportions by mass of dolomite relative to calcite mineral weathering (e.g., Mg²⁺/Ca²⁺ mole ratio of 0.33). The HCO₃ ^? concentration and pCO₂ values increase as soil thickness and alluvium increase for discrete spring samples, which are near equilibrium with respect to calcite. Typically, this results in approximately 1.5 meq/l increase in HCO₃ ^? from the alpine to the dinaric karst regions. Streams in general do not change in HCO₃ ^?, Mg²⁺/Ca²⁺, or Mg²⁺/HCO₃ ^? concentrations down course, but warming and degassing of CO₂ produce high degrees of supersaturation with respect to calcite. Carbonate-weathering intensity (mmol/km²-s) is highest within the alpine regions where stream discharge values range widely to extreme values during spring snowmelt. Overall, the elemental fluxes of HCO₃ ^?, Ca²⁺, and Mg²⁺ from the tributary watersheds are proportional to the total water flux because carbonates dissolve rapidly to near equilibrium. Importantly, dolomite weathers preferentially over calcite except for pure limestone catchments.     

Reconciling the elemental and Sr isotope composition of Himalayan weathering fluxes: insights from the carbonate geochemistry of stream waters

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 (P_CO2, 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 P_CO2 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 P_CO2 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.     

Formation of modern dolomite in hypersaline pans of the Western Cape,South Africa

Authigenic calcite and dolomite and biogenic aragonite occur in Holocene pan sediments in a Mediterranean‐type climate on the western coastal plain of South Africa. Sediment was analysed from a Late Pleistocene coastal pan at Yzerfontein and four Holocene inland pans ranging from brackish to hypersaline. The pans are between 0·08 and 0·14 km² in size. The δ¹⁸O_PDB values of carbonate minerals in the pan sediments range from ?2·41 to 5·56‰ and indicate precipitation from evaporative waters. Covariance of total organic content and percentage carbonate minerals, and the δ¹³C_PDB values of pan carbonate minerals (?8·85 to ?1·54‰) suggest that organic matter degradation is a significant source of carbonate ions. The precipitation of the carbonate minerals, especially dolomite, appears to be mediated by sulphate‐reducing bacteria in the black sulphidic mud zone found in the brine‐type hypersaline pans. The knobbly, sub‐spherical texture of the carbonate minerals suggests that the precipitation of the carbonate minerals, particularly dolomite, is related to microbial processes. The ⁸⁷Sr/⁸⁶Sr ratios of pan carbonate minerals (0·7108 to 0·7116) are slightly higher than modern sea water and indicate a predominantly sea water (marine aerosol) source for calcium (Ca²⁺) ions with relatively minor amounts of Ca²⁺ derived from the chemical weathering of bedrock.     

Silicate and carbonate mineral weathering in soil profiles developed on Pleistocene glacial drift (Michigan, USA): Mass balances based on soil water geochemistry

Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition.Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO₂. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg²⁺/Ca²⁺ ratio of 0.4.Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca²⁺ and Mg²⁺ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg²⁺ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.     

室温条件下青海湖水中镁离子浓度对沉淀碳酸钙同质多像类型的调控

青海湖是我国唯一报道过的现代湖底沉积物中白云石、方解石和文石等多种碳酸盐矿物共存的高原内陆咸水湖泊.以青海湖水和除菌青海湖水作为载体,以CaCl2和MgCl2·6 H2O作为反应原料,在实验室常温条件下采取控制变量法制备出不同浓度Mg2+参与下的钙质沉淀物,探讨Mg2+浓度对沉淀物类型的影响.仅添加CaCl2时,青海湖...     

Microbially influenced formation of Mg‐calcite and Ca‐dolomite in the presence of exopolymeric substances produced by sulphate‐reducing bacteria

Some species of sulphate‐reducing bacteria (SRB) are known to mediate the formation of dolomite and Mg‐calcite. However, their exact role in the mineralization process remains elusive. Here, we present the result of a laboratory experiment that was designed to test whether formation of carbonate minerals by SRB can occur in the absence of living cells, through passive mineralization of their exopolymeric substances (EPS). SRB capable of mediating dolomite were cultivated in the laboratory, allowing them to secrete EPS. Microbial activity within the cultures was subsequently inhibited with antibiotics. Only after this step, Ca²⁺ and Mg²⁺ were added to the solution and carbonate minerals could form. Mg‐calcite and disordered Ca‐dolomite precipitated in association with EPS. The mol.% of Mg²⁺ in the crystals increased with longer incubation times. This result demonstrates that organic compounds produced by SRB can mediate the formation of Ca‐Mg carbonates in the absence of an active metabolism.     

Mineralogy,nucleation and growth of dolomite in the laboratory and sedimentary environment: A review

Dolomite [CaMg(CO₃)₂] forms in numerous geological settings, usually as a diagenetic replacement of limestone, and is an important component of petroleum reservoir rocks, rocks hosting base metal deposits and fresh water aquifers. Dolomite is a rhombohedral carbonate with a structure consisting of an ordered arrangement of alternating layers of Ca²⁺ and Mg²⁺ cations interspersed with anion layers normal to the c‐axis. Dolomite has symmetry, lower than the (CaCO₃) symmetry of calcite primarily due to Ca–Mg ordering. High‐magnesium calcite also has symmetry and differs from dolomite in that Ca²⁺ and Mg²⁺ ions are not ordered. High‐magnesium calcite with near‐dolomite stoichiometry (≈50 mol% MgCO₃) has been observed both in nature and in laboratory products and is referred to in the literature as protodolomite or very high‐magnesium calcite. Many dolomites display some degree of cation disorder (Ca²⁺ on Mg²⁺ sites and vice versa), which is detectable using transmission electron microscopy and X‐ray diffractometry. Laboratory syntheses at high temperature and pressure, as well as studies of natural dolomites show that factors affecting dolomite ordering, stoichiometry, nucleation and growth include temperature, alkalinity, pH, concentration of Mg and Ca, Mg to Ca ratio, fluid to rock ratio, mineralogy of the carbonate being replaced, and surface area available for nucleation. In spite of numerous attempts, dolomite has not been synthesized in the laboratory under near‐surface conditions. Examination of published X‐ray diffraction data demonstrates that assertions of dolomite synthesis in the laboratory under near‐ambient conditions by microbial mediation are unsubstantiated. These laboratory products show no evidence of cation ordering and appear to be very high‐magnesium calcite. Elevated‐temperature and elevated‐pressure experiments demonstrate that dolomite nucleation and growth always are preceded by very high‐magnesium calcite formation. It remains to be demonstrated whether microbial‐mediated growth of very high‐magnesium calcite in nature provides a precursor to dolomite nucleation and growth analogous to reaction paths in high‐temperature experiments.     

Carbonate stromatolites from a Messinian hypersaline setting in the Caltanissetta Basin, Sicily: petrographic evidence of microbial activity and related stable isotope and rare earth element signatures

Lower Messinian stromatolites of the Calcare di Base Formation at Sutera in Sicily record periods of low sea‐level, strong evaporation and elevated salinity, thought to be associated with the onset of the Messinian Salinity Crisis. Overlying aragonitic limestones were precipitated in normal to slightly evaporative conditions, occasionally influenced by an influx of meteoric water. Evidence of bacterial involvement in carbonate formation is recorded in three dolomite‐rich stromatolite beds in the lower portion of the section that contain low domes with irregular crinkly millimetre‐scale lamination and small fenestrae. The dominant microfabrics are: (i) peloidal and clotted dolomicrite with calcite‐filled fenestrae; (ii) dolomicrite with bacterium‐like filaments and pores partially filled by calcite or black amorphous matter; and (iii) micrite in which fenestrae alternate with dark thin wispy micrite. The filaments resemble Beggiatoa‐like sulphur bacteria. Under scanning electron microscopy, the filaments consist of spherical aggregates of dolomite, interpreted to result from calcification of bacterial microcolonies. The dolomite crystals are commonly arranged as rounded grains that appear to be incorporated or absorbed into developing crystal faces. Biofilm‐like remains occur in voids between the filaments. The dolomite consistently shows negative δ¹³C values (down to ?11·3‰) and very positive δ¹⁸O (mean value 7·9‰) that suggest formation as primary precipitate with a substantial contribution of organic CO₂. Very negative δ¹³C values (down to ?31·6‰) of early diagenetic calcite associated with the dolomite suggest contribution of CO₂ originating by anaerobic methane oxidation. The shale‐normalized rare earth element patterns of Sutera stromatolites show features similar to those in present‐day microbial mats with enrichment in light rare earth elements, and M‐type tetrad effects (enrichment around Pr coupled to a decline around Nd and a peak around Sm and Eu). Taken together, the petrography and geochemistry of the Sutera stromatolites provide diverse and compelling evidence for microbial influence on carbonate precipitation.     

Geochemical controls on a calcite precipitating spring

A small spring fed stream was found to precipitate calcite by mainly inorganic processes and in a nonuniform manner. The spring water originated by rainwater falling in a 0.8 km² basin, infiltrating, and dissolving calcite and dolomite followed by dissolution of gypsum or anhydrite. The Ca²⁺/Mg²⁺ indicates that calcite is probably precipitated in the subsurface from a supersaturated solution. This water emerges from the spring still about 5 times supersaturated with respect to calcite and continues calcite precipitation. When 10 times supersaturation is reached, due to CO₂ degassing the precipitation is more rapid. The calcite accumulation from the stream with a flow of 5 l/s is calculated to be 12600 kg/yr with the highest rates in areas where CO₂ degassing is the greatest. The non-equilibrium, as shown by the high calcite supersaturation, is also reflected in a variable partitioning pattern for Sr²⁺ between the water and calcite.     

The dolomitization of CaCO3: an experimental study at 252–295°C

The results of experiments on the hydrothermal dolomitization of calcite (between 252 and 295°C) and aragonite (at 252°C) by a 2 M CaCl₂-MgCl₂ aqueous solution are reported and discussed. Dolomitization of calcite proceeds via an intermediate high (ca. 35 mole %) magnesian calcite, whereas that of aragonite is carried out through the conversion of the reactant into a low (5.6 mole %) magnesian calcite which in turn transforms into a high (39.6 mole %) magnesian calcite. Both the intermediate phases and dolomite crystallize through a dissolution-precipitation reaction. The intermediate phases form under local equilibrium within a reaction zone surrounding the dissolving reactant grains. The volume of the reaction zone solution can be estimated from Sr²⁺ and Mg²⁺ partitioning equations. In the case of low magnesian calcite growing at the expense of aragonite at 252°C, the total volume of these zones is in the range of 2 × 10^?5 to 2 × 10^?4 1., out of 5 × 10^?3 1., the volume of the bulk solution.The apparent activation energies for the initial crystallization of high magnesian calcite and dolomite are 48 and 49 kcal/mole, respectively.Calcite transforms completely into dolomite within 100 hr at 252°C. The overall reaction time is reduced to approximately 4 hr at 295°C. The transformation of aragonite to dolomite at 252°C occurs within 24 hr. The nature of the reactant dictates the relative rates of crystallization of the intermediate phases and dolomite. With calcite as reactant, dolomite growth is faster than that of magnesian calcite; this situation is reversed when aragonite is dolomitized.Coprecipitation of Sr²⁺ with dolomite is independent of temperature (within analytical error) between 252 and 295°C. Its partitioning, with respect to calcium, between dolomite and solution results in distribution coefficients in the range of 2.31 × 10^?2 to 2.78 × 10^?2.     

A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

The rate of Cd²⁺ sorption by calcite was determined as a function of pH and Mg²⁺ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO₃. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca²⁺ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd²⁺ sorption decrease with increasing pH or with increasing Mg²⁺. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer.A model is presented which is consistent with the rates of Cd²⁺ sorption and Ca²⁺ isotopic exchange. In the model, the first step in Cd²⁺ sorption involves a fast adsorption reaction that is followed by diffusion of Cd²⁺ into a surface layer of hydrated CaCO₃ that overlies crystalline calcite. Desorption of Cd²⁺ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO₃, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution.     

Discovery of galena in Tertiary pebbly coquina and its implication in mineralization

A suite of terrestrial-marine transitional carbonate beds occur in the Lower Tertiary of the Kuqa Basin, Xinjiang. The pebbly coquina, Paleocene in age, is distributed along the southern pediment of the Tianshan Mountains north of Baicheng, where Pb-mineralization has been observed for the first time. The pebbly coquina consists of well-rounded quartzitic pebbles, quartz sands, shell fossils, shell fragments and equigranular fecal pellets. Four types of carbonate minerals have been revealed: 1) euhedral dolomite (Mg₆₀Ca₄₀)CO₃, 2) anhedral dolomite (Mg₅₇Ca₄₃)CO₃, 3) dolomitic calcite (Mg₂₀Ca₈₀)CO₃ and magnesitic dolomite with a trace amount of Pb(Mg₇₃Ca₂₇)CO₃. Five types of galena filling the pebbly coquina have been found: 1) in the shell tower end, 2) on the inner shell wall, 3) on the outer shell wall, 4) around the shell wall, and 5) among shell fragments. The galena replacement took place mainly in the early stage of diagenesis. Stable isotope analyses show (δ¹³C values range from −0.8 to +2.3 and δ¹⁸O values from −0.1 to +0.5, indicating a marine environment under the influence of fresh water, which is consistent with the result of megascopic facies analysis in paleogeography. It is concluded that the discovery of galena in the Tertiary pebbly coquina in the north of Baicheng, Xinjiang may provide new clues to the searching for strata-bound Pb-Zn deposits in the vast area of northern Tarim Basin.     

Geology and C-O isotope geochemistry of carbonate-hosted Pb-Zn deposits, NW Guizhou Province, SW China

The Pb-Zn metallogenic district in NW Guizhou Province is an important part of the Yun-nan-Sichuan-Guizhou Pb-Zn metallogenic province, and also is one of the most important Pb-Zn producers in China. The hosting rocks of the Pb-Zn deposits are Devonian to Permian carbonate rocks, and the basement rocks are meta-sedimentary and igneous rocks of the Proterozoic Kunyang and Huili groups. The ore minerals are composed of sphalerite, galena and pyrite, and the gangue minerals are include calcite and dolomite. Geology and C-O isotope of these deposits were studied in this paper. The results show that δ13C and δ18O values of hydrothermal calcite, altered wall rocks-dolostone, sedimentary calcite and hosting carbonate rocks range from -5.3‰ to -0.6 ‰ (mean -3.4‰) and +11.3‰ to +20.9 ‰ (mean +17.2‰), -3.0‰ to +0.9 ‰ (mean -1.3‰) and +17.0‰ to +20.8‰ (mean +19.7‰), +0.6‰ to +2.5 ‰ (mean +1.4‰) and +23.4‰ to +26.5 ‰ (mean +24.6‰), and -1.8‰ to +3.9‰ (mean +0.7‰) and +21.0‰ to +26.8‰ (mean +22.9‰), respectively, implying that CO2 in the ore-forming fluids was mainly a result of dissolution of Devonian and Carboniferous carbonate rocks. However, it is difficult to evaluate the contribution of sediment de-hydroxylation. Based on the integrated analysis of geology, C and O isotopes, it is believed that the ore-forming fluids of these carbonate-hosted Pb-Zn deposits in this area were derived from multiple sources, including hosting carbonate rocks, Devonian to Permian sedimentary rocks and basement rocks (the Kun-yang and Huili groups). Therefore, the fluids mixing is the main precipitation mechanism of the Pb-Zn deposit in this province.     

Diagenetic crystallization and oxidation of siderite in red bed (Buntsandstein) sediments from the Central Iberian Chain,Spain

Compactional deformation facilitated replacement of dolomite and calcite by siderite and its subsequent oxidation in carbonate cemented red beds of the Triassic Buntsandstein in the Iberian Chain. Locally, the sedimentary clasts were cemented by carbonate that was derived from dissolution of locally exposed dolomite in the basement. Microstructures indicate that during sedimentation of the rocks, oxidizing conditions prevailed in the sediments and the basement was reddened by impregnation of hematite. Reducing conditions prevailed during deformation of the sediments. Ferric iron was reduced to Fe²⁺, that reacted with deformed dolomite and calcite cement to produce fine grained siderite. At a later stage, siderite crystallites were (partly) oxidized to form a secondary phase of brown ferric oxide (goethite). Locally, goethite transformed to fine grained hematite that caused secondary reddening of the sediments. The reactions are associated with a combined volume loss of the solid phases of c. 50% per reaction mol; this was accommodated by the formation of pores. Oxidation of siderite was associated with release of CO₂; localized dissolution took place of feldspar and concurrently growth of kaolinite occurred by acidifying condition during release of CO₂. The relation of redox reactions and deformation is comparable to those in red bed conglomerates in the region. Reductive dissolution occurred at sites of stress concentration, particularly at contact points of pebbles. Late stage precipitation of ferric oxides and pyrolusite took place at oxidizing conditions in association with uplift.     

Hydrogeochemistry of groundwater and anthropogenic control over dolomitization reactions in alluvial sediments of the Deoria district: Ganga plain,India

Groundwater is a critical resource in Deoria district, as it is the main source of drinking water and irrigation. The aquifer has deteriorated to a high degree, during the last two to three decades, in quality and quantity due to high population growth and environmental pollution. More than 90% of the population get their drinking water from subsurface waters. Fifteen wells were sampled in June 2006 to probe the hydrogeochemical components that influence the water quality. The results show that groundwater have EC, TDS, Na⁺, Mg²⁺, HCO₃⁻ and TH higher than the WHO, 1997 maximum desirable limits. A hydrogeochemical numerical model for carbonate minerals was constructed using the PHREEQC package. The regression analysis shows that there are three groups of elements which are significantly and positively correlated. The main hydrochemical facies of the aquifer (Ca + Mg–HCO₃) represents 33.33% of the total wells. The geochemical modeling demonstrated that the reactions responsible for the hydrochemical evolution in the area fall into three categories: (1) dissolution of salts, (2) precipitation of dolomite, (3) ion exchange. Solubility of dolomite, calcite, aragonite and gypsum were assessed in terms of the saturation index. The thermodynamic prerequisites for dolomite supersaturation reactions are satisfied by subsurface waters, since they are supersaturated with respect to dolomite, undersaturated (or in equilibrium) with respect to calcite, and undersaturated with respect to gypsum. The Ca²⁺ versus SO₄²⁻ and Mg²⁺ versus SO₄²⁻ trends are also compatible with homologous trends resulting from dolomite supersaturation.     

Isotopic and Chemical Constraints on the Biogeochemistry of Dissolved Inorganic Carbon and Chemical Weathering in the Karst Watershed of Krka River (Slovenia)

The hydrogeochemical and carbon isotope characteristics of the Krka River, Slovenia, were investigated to estimate the carbon transfer from the land ecosystem in the watershed. During the 3-year sampling period (2008–2010), temperature, pH, electrical conductivity, major ion content, dissolved inorganic carbon (DIC) and dissolved organic carbon content, and the isotopic composition of DIC (δ¹³C_DIC) were monitored in the main stream of the Krka River and its tributaries. The major solute composition of analysed waters is dominated by an input of HCO₃ ^?, Ca²⁺ and Mg²⁺ originating from carbonate dissolution. The Mg²⁺/Ca²⁺ and Mg²⁺/HCO₃ ^? molar ratio values ranging from 0.24 to 0.71 and 0.05 to 0.30, respectively, indicate a high degree of dolomite dissolution relative to calcite. Dissolved CO₂ concentrations in the river were up to tenfold supersaturated relative to the atmosphere, resulting in supersaturation with respect to calcite and degassing of CO₂ downstream. The δ¹³C values in river water range from ?15.6 to ?9.4 ‰ and are controlled by the input of tributaries, exchange with atmospheric CO₂, degradation of organic matter, and dissolution of carbonates. The mass balance calculations for riverine DIC suggest that the contribution from carbonate dissolution and degradation of organic matter have major influence, whereas the exchange with atmospheric CO₂ has minor influence on the inorganic carbon pool in the Krka River.     

Effects of freshwater Synechococcus sp. cyanobacteria pH buffering on CaCO3 precipitation: Implications for CO2 sequestration

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.     

'Forbidden zone' subduction of sediments to 150 km depth— the reaction of dolomite to magnesite + aragonite in the UHPM metapelites from western Tianshan, China

The solid‐state reaction magnesite (MgCO₃) + calcite (aragonite) (CaCO₃) = dolomite (CaMg(CO₃)₂) has been identified in metapelites from western Tianshan, China. Petrological studies show that two metamorphic stages are recorded in the metapelites: (1) the peak mineral assemblage of magnesite and calcite pseudomorphs after aragonite which is only preserved as inclusions within dolomite; and (2) the retrograde glaucophane‐chloritoid facies mineral assemblage of glaucophane, chloritoid, dolomite, garnet, paragonite, chlorite and quartz. The peak metamorphic temperatures and pressures are calculated to be 560–600 °C, 4.95–5.07 GPa based on the calcite–dolomite geothermometer and the equilibrium calculation of the reaction dolomite = magnesite + aragonite, respectively. These give direct evidence in UHP metamorphic rocks from Tianshan, China, that carbonate sediments were subducted to greater than 150 km depth. This UHP metamorphism represents a geotherm lower than any previously estimated for subduction metamorphism (< 3.7 °C km^?1) and is within what was previously considered a ‘forbidden’ condition within Earth. In terms of the carbon cycle, this demonstrates that carbonate sediments can be subducted to at least 150 km depth without releasing significant CO₂ to the overlying mantle wedge.