Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^–1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^–1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

Effects of seed material and solution composition on calcite precipitation

We studied the effects of seed material and solution composition on calcite crystal precipitation using a pH-stat system. The seed materials investigated included quartz, dolomite, two calcites with different particle size and specific surface area, and two dried precipitates from precipitative softening water treatment plants. Our results indicated that, of the seed materials examined, only calcite had the ability to initiate calcite precipitation in a solution with a degree of supersaturation of 5.3 over a period of two hours, and that the precipitation rate was proportional to the available surface area of the seed. For different solution compositions with the same degree of supersaturation, the calcite precipitation rate increased with increasing carbonate/calcium ratio, which contradicts the generally accepted empirical rate expression that the degree of supersaturation is the sole factor controlling precipitation kinetics. By applying a surface complexation model, the surface concentrations of two species, >CO₃⁻ and >CaCO₃⁻, appear to be responsible for catalyzing calcite precipitation.     

Dissolved carbon in pore waters from the carbonate barrier reef of Tahiti (French Polynesia) and its basalt basement

This paper deals with dissolved inorganic carbon (DIC) and organic carbon (DOC) in pore waters from a 150 m deep hole drilled through the carbonate barrier reef of Tahiti and its underlying basalt basement. Alkalinity-pH measurements were used to calculate the DIC species concentration, and DOC was analysed according to the high temperature catalytic oxidation technique. Salinity was used as a conservative tracer to help identify water origin and mixing within the hole. Water mixing, calcium carbonate dissolution and mineralization of organic carbon combined to form three distinct groups of pore water. In the deeper basalt layers, pore water with alkalinity of 1.4 meq kg^?1 pH of 7.6 and p(CO₂) of 1.2 mAtm was undersaturated with respect to both aragonite and calcite. In the intermediate carbonate layer, pore water with alkalinity of more than 2.0 meq kg^?1, pH of 7.70 and p(CO₂) of 1.4 mAtm was supersaturated with respect to both aragonite and calcite. The transition zone between those two groups extended between 80 and 100 m depth. The shift from aragonite undersaturation to supersaturation was mainly attributed to the mixing of undersaturated pore waters from the basalt basement with supersaturated pore waters from the overlaying limestone. In the top of the reef, inputs from a brackish water lens further increased p(CO₂) up to 5.6 times the atmospheric P(CO₂).     

A study of oxygen isotopic fractionation during bio-induced calcite precipitation in eutrophic Baldeggersee,Switzerland

In order to better understand environmental factors controlling oxygen isotope shifts in autochthonous lacustrine carbonate sequences, we undertook an extensive one-year study (March, 1995 to February, 1996) of water-column chemistry and daily sediment trap material from a small lake in Central Switzerland. Comparisons between calculated equilibrium isotope values, using the fractionation equation of Friedman and O’Neil, (1977) and measured oxygen isotope ratios of calcite in the sediment-traps reveal that oxygen isotopic values of autochthonous calcite (δ¹⁸O) are in isotopic equilibrium with ambient water during most of the spring and summer, when the majority of the calcite precipitates. In contrast, small amounts of calcite precipitated in early-spring and again in late-autumn are isotopically depleted in ¹⁸O relative to the calculated equilibrium values, by as much as 0.8‰. This seasonally occurring apparent isotopic nonequilibrium is associated with times of high phosphorous concentrations, elevated pH (∼8.6) and increased [CO₃²⁻] (∼50 μmol/l) in the surface waters. The resulting weighted average δ¹⁸O value for the studied period is −9.6‰, compared with a calculated equilibrium δ¹⁸O value of −9.4‰. These data convincingly demonstrate that δ¹⁸O of calcite are, for the most part, a very reliable proxy for temperature and δ¹⁸O of the water.     

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.     

Carbon and Oxygen Isotopic Composition of Surface‐Sediment Carbonate in Bosten Lake (Xinjiang,China) and its Controlling Factors

Bosten Lake is a mid-latitude lake with water mainly supplied by melting ice and snow in the Tianshan Mountains. The depositional environment of the lake is spatially not uniform due to the proximity of the major inlet and the single outlet in the western part of the lake. The analytical results show that the carbon and oxygen isotopic composition of recent lake sediments is related to this specific lacustrine depositional environment and to the resulting carbonate mineralogy. In the southwestern lake region between the Kaidu River inlet and the Kongqi River outlet, carbon isotope composition (δ13C) values of the carbonate sediment (?1‰ to ?2‰) have no relation to the oxygen isotope composition of the carbonate (δ18O) values (?7‰ to ?8‰), with both isotopes showing a low variability. The carbonate content is low (<20%). Carbonate minerals analyzed by X-ray diffraction are mainly composed of calcite, while aragonite was not recorded. The salinity of the lake water is low in the estuary region as a result of the Kaidu River inflow. In comparison, the carbon and oxygen isotope values are higher in the middle and eastern parts of the lake, with δ13C values between approximately +0.5‰ and +3‰, and δ18O values between ?1‰ and ?5‰. There is a moderate correlation between the stable oxygen and carbon isotopes, with a coefficient of correlation r of approximately 0.63. This implies that the lake water has a relatively short residence time. Carbonate minerals constitute calcite and aragonite in the middle and eastern region of the lake. Aragonite and Mg–calcite are formed at higher lake water salinity and temperatures, and larger evaporation effects. More saline lake water in the middle and eastern region of the lake and the enhanced isotopic equilibrium between water and atmospheric CO2 cause the correlating carbon and oxygen isotope values determined for aragonite and Mg–calcite. Evaporation and biological processes are the main reasons for the salinity and carbonate mineralogy influence of the surface-sediment carbonate in Bosten Lake. The lake water residence time and the CO2 exchange between the atmosphere and the water body control the carbon and oxygen isotope composition of the carbonate sediment. In addition, organic matter pollution and decomposition result in the abnormally low carbon isotope values of the lake surface-sediment carbonate.     

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.     

Surface carbonate and land-derived clastic marine sediments from southern Chile: mineralogical and geochemical investigation

Surface carbonate and land-derived deposits in the sea off southern Chile were investigated for their mineralogical and geochemical composition. The data were related to environmental features and compared with those of similar temperate and polar carbonate deposits from Tasmania, New Zealand, Arctica, and Antarctica. The mineralogy of the siliciclastic fraction is typical of cold areas and is mainly composed of chlorite, mica, quartz, feldspars and amphibole. The CaCO₃ content varies from 30 to 90%; carbonate mineralogy is made up of low-Mg calcite, high-Mg calcite and minor amounts of aragonite. The Ca, Mg, Sr, Fe, and Mn contents of bulk carbonates and some selected skeletal hard parts are comparable to those of carbonates from Tasmania. The elemental composition is mainly related to carbonate mineralogy, skeletal components, and seawater conditions. The δ¹³C and δ¹⁸O values of carbonates are positive, and their field falls between the “seafloor diagenesis” and “upwelling water” trend lines, because the sediments are likely to be in equilibrium with waters of Antarctic origin. The mineralogical, elemental, and isotopic compositions of carbonates from southern Chile show better similarities with the “temperate” carbonates from Tasmania and New Zealand than with the “polar” carbonates from Arctica and Antarctica. Carbonate deposition is allowed by the low terrigenous input, the low SPM concentration and, probably, the upwelling of seawater from Antarctica.     

Impact of Carbonate Precipitation on Riverine Inorganic Carbon Mass Transport from a Mid-continent, Forested Watershed

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

Petrological and isotopic implications of some contrasting Late Precambrian carbonates, NE Spitsbergen

The dominantly shallow-marine Vendian succession of NE Spitsbergen contains distinctive types of carbonate rock. Limestones deposited before Vendian glaciation resemble those described from other Upper Proterozoic successions, being high in Sr and inferred to have been originally aragonitic, including the distinctive 5–10 Jim equant polygonal calcite of cemented shrinkage cracks. In contrast, manganoan stromatolitic limestones within marginal-marine glacial-outwash deposits, and consisting of micrite, microspar and fascicular-optic calcite are interpreted as originally calcitic. The restriction of primary marine calcite to cold seawater is comparable with Recent and Permian carbonates, although the Precambrian example formed in a sea diluted with meltwater. There is good textural preservation of relatively ¹⁸O-rich oolitic dolostones which were cemented in a supratidal environment by artesian fluids. Nevertheless, early diagenetic replacement is inferred, immediately prior to a glacial episode. Post-glacial dolostones are either replacive marine, or evaporative lacustrine, but share rather more negative δ¹⁸O values, closer to the mean of Late Precambrian dolostones. The heaviest oxygen isotope values constrain seawater δ¹⁸O to no more negative than — 2 to — 4_SMOW. The main reason for the pronounced oxygen isotopic depletion of most Late Precambrian carbonates is their initial metastable mineralogy. The possibility of determining palaeolatitudes of the enigmatic widespread Late Proterozoic glaciations by isotopic analysis of freshwater periglacial calcareous precipitates is raised. Significant carbon isotope variations reflect changes in depositional water chemistry: some of these could be global in extent.     

Unusual isotopic phenomena in Welsh quarry water and carbonate crusts

Modern terrestrial speleothem-like calcareous deposits in streams draining a disused lime quarry on Black Mountain, South Wales have anomalously negative δ¹⁸O and δ¹³C compositions compared with other similar European deposits. Black Mountain water chemistry is unusual only in its locally very high pH (> 11.5) and carbonate ion concentrations. The high pH is caused by dissolution of lime spoil, resulting in high OH^– concentrations. This high alkalinity causes uptake of atmospheric CO₂ and strong fractionation of both carbon and oxygen stable isotopes, resulting in calcite precipitates with unusually negative isotopic compositions. Since shifts in δ¹⁸O of < 1° are highly significant for Holocene palaeoclimate reconstructions, depletions caused by hyperalkaline waters must be avoided. While extreme lime spoil contamination should be obvious, less heavily affected sites will record smaller fractionation effects and might escape detection. Even small depletions from low-level contamination will have large effects on palaeotemperatures based on carbonate crust δ¹⁸O values.     

Cave air control on dripwater geochemistry, Obir Caves (Austria): Implications for speleothem deposition in dynamically ventilated caves

There are very few process studies that demonstrate the annual variation in cave environments depositing speleothems. Accordingly, we initiated a monitoring program at the Obir Caves, an Austrian dripstone cave system characterized by a seasonally changing air flow that results in a predictable pattern of high pCO₂ during summer and low pCO₂ in winter. Although similar seasonal changes in soil pCO₂ occur, they are not directly connected with the changes in the subsurface since the dripwaters are fed from a well-mixed source showing little seasonal variation. Cold season flushing by relatively CO₂-poor air enhances degassing of CO₂ in the cave and leads to a high degree of supersaturation of dripwater with regard to calcite. Forced calcite deposition during the cold season also gives rise to a pronounced pattern of synchronous seasonal variations in electrical conductivity, alkalinity, pH, Ca and δ¹³C_DIC which parallel variations recorded in δ¹³C_{cave air}. Chemical components unaffected by calcite precipitation (e.g., δD, δ¹⁸O, SiO₂, SO₄) lack a seasonal signal attesting to a long residence in the karst aquifer. Modeling shows that degassing of CO₂ from seepage waters results in kinetically-enhanced C isotopic fractionation, which contrasts with the equilibrium degassing shown from the Soreq cave in Israel. The Obir Caves may serve as a case example of a dripstone cave whose seepage waters (and speleothems) show intra-annual geochemical variability that is primarily due to chemical modification of the groundwater by a dynamic, bidirectional subsurface air circulation.     

The geochemical origin of sepiolite and kerolite at Amboseli,Kenya

A massive white sepiolite deposit at Amboseli precipitated from magnesium and silica released during the ground water dolomitization of an earlier lacustrine sepiolite. Kerolite has since formed in proximity to the massive sepiolite as an alteration product of sepiolite and as a ground water precipitate when the pH is below 8. Authigenic sepiolite also occurs in the overlying younger sediments. Kerolite is likely to occur but has not yet been positively identified.Presently, ground waters within the Amboseli Basin are supersaturated with respect to sepiolite and kerolite. This supersaturation results from the weathering of alkaline olivine basalts on the edge of the basin. The precipitation of sepiolite and/or kerolite does not control ground water compositions in the basin. These reactions are slow compared to other aqueous-mineral reactions such as those maintaining carbonate mineral equilibria. Equilibrium between disordered-dolomite and calcite buffers the log a _Mg2+/(a _H+)² as a function of log f _{CO 2} in ground waters in the proximity of the massive sepiolite. This reaction can help explain the presence of sepiolite associated with dolomites in other near-surface deposits besides Amboseli.     

Multi-proxy approach (H/H, O/O, C/C and Sr/Sr) for the evolution of carbonate-rich groundwater in basalt dominated aquifer of Axum area, northern Ethiopia

Isotopic and chemical composition of groundwater from wells and springs, and surface water from the basalt-dominated Axum area (northern Ethiopia) provides evidence for the origin of water and dissolved species. Shallow (depth < 40 m) and deep groundwater are distinguished by both chemical and isotopic composition. Deep groundwater is significantly enriched in dissolved inorganic carbon up to 40 mmol l⁻¹ and in concentrations of Ca²⁺, Mg²⁺, Na⁺ and Si(OH)₄ compared to the shallow type.The δ²H and δ¹⁸O values of all solutions clearly indicate meteoric origin. Shifts from the local meteoric water line are attributed to evaporation of surface and spring water, and to strong water–rock interaction. The δ¹³C_DIC values of shallow groundwater between −12 and −7‰ (VPDB) display the uptake of CO₂ from local soil horizons, whereas δ¹³C_DIC of deep groundwater ranges from −5 to +1‰. Considering open system conditions with respect to gaseous CO₂, δ¹³C_DIC = +1‰ of the deep groundwater with highest PCO₂ = 10^−0.9 atm yields δ¹³C_CO2(gas) ≈ −5‰, which is close to the stable carbon isotopic composition of magmatic CO₂. Accordingly, stable carbon isotope ratios within the above range are referred to individual proportions of CO₂ from soil and magmatic origin. The uptake of magmatic CO₂ results in elevated cations and Si(OH)₄ concentrations. Weathering of local basalts is documented by ⁸⁷Sr/⁸⁶Sr ratios of the groundwater from 0.7038 to 0.7059. Highest values indicate Sr release from the basement rocks. Besides weathering of silicates, neoformation of solids has to be considered, which results in the formation of, e.g., kaolinite and montmorillonite. In several solutions supersaturation with respect to calcite is reached by outgassing of CO₂ from the solution leading to secondary calcite formation.     

Recharge in northern clime calcareous sandy soils: soil water chemical and carbon-14 evolution

Chemical analyses were performed on soil water extracted from two cores taken from a sandy calcareous soil near Delhi, Ontario. Calcite saturation is attained within the unsaturated zone over short distances and short periods of time, whereas dolomite undersaturation persists to the groundwater table. The progressive dissolution of dolomite by soil water, within the unsaturated zone, after calcite saturation is reached results in calcite supersaturation.Deposition of iron and manganese oxyhydroxide phases occurs at the carbonate leached/unleached zone boundary. This is a result of soil water neutralization due to carbonate dissolution during infiltration but may also reflect the increased rate of oxidation of dissolved ferrous and manganous ions at higher pH's. The role of bacteria in this process has not been investigated.The depth of the carbonate leached/unleached zone boundary in a calcareous soil has important implications for ¹⁴C groundwater dating. The depth of this interface at the study site (?2 m) does not appear to limit ¹⁴C diffusion from the root zone to the depth at which carbonate dissolution occurs. Thus, soil water achieves open system isotopic equilibrium with the soil CO₂ gas phase. It is calculated that in soils with similar physical properties to the study soil but with depths of leaching of 5 m or more, complete ¹⁴C isotopic equilibration of soil water with soil gas would not occur. Soil water, under these conditions would recharge to the groundwater exhibiting some degree of closed system ¹⁴C isotopic evolution.     

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.     

Stable isotope variations in modern tropical speleothems: Evaluating equilibrium vs. kinetic isotope effects

Applications of speleothem calcite geochemistry in climate change studies require the evaluation of the accuracy and sensitivity of speleothem proxies to correctly infer paleoclimatic information. The present study of Harrison’s Cave, Barbados, uses the analysis of the modern climatology and groundwater system to evaluate controls on the C and O isotopic composition of modern speleothems. This new approach directly compares the δ¹⁸O and δ¹³C values of modern speleothems with the values for their corresponding drip waters in order to assess the degree to which isotopic equilibrium is achieved during calcite precipitation. If modern speleothems can be demonstrated to precipitate in isotopic equilibrium, then ancient speleothems, suitable for paleoclimatic studies, from the same cave environment may also have been precipitated in isotopic equilibrium. If modern speleothems are precipitated out of isotopic equilibrium, then the magnitude and direction of the C and O isotopic offsets may allow specific kinetic and/or equilibrium isotopic fractionation mechanisms to be identified.Carbon isotope values for the majority of modern speleothem samples from Harrison’s Cave fall within the range of equilibrium values predicted from the combined use of (1) calcite-water fractionation factors from the literature, (2) measured temperatures, and (3) measured δ¹³C values of the dissolved inorganic carbon of drip waters. Calcite samples range from ∼0.8‰ higher to ∼1.1‰ lower than predicted values. The ¹³C depletions are likely caused by kinetically driven departures in the fractionation between HCO₃⁻ (aq) and CaCO₃ from equilibrium conditions, caused by rapid calcite growth. ¹³C enrichments can be accounted for by Rayleigh distillation of the HCO₃⁻ (aq) reservoir during degassing of ¹³C-depleted CO₂.Modern speleothems from Harrison’s Cave are not in O isotopic equilibrium with their corresponding drip waters and are 0.2‰ to 2.3‰ enriched in ¹⁸O relative to equilibrium values. δ¹⁸O variations in modern calcite are likely controlled by kinetically driven changes in the fractionation between HCO₃⁻ (aq) and CaCO₃ from equilibrium conditions to nonequilibrium conditions, consistent with rapid calcite growth. In contrast to δ¹³C, δ¹⁸O values of modern calcite may not be affected by Rayleigh distillation during degassing because CO₂ hydration and hydroxylation reactions will buffer the O isotopic composition of the HCO₃⁻ (aq) reservoir. If the effects of Rayleigh distillation manifest themselves in the O isotopic system, they will result in ¹⁸O enrichment in the HCO₃⁻ (aq) reservoir and ultimately in the precipitated CaCO₃.     

The role of sulfate groups in controlling CaCO3 polymorphism

The nucleation and growth of CaCO₃ phases from aqueous solutions with SO₄²⁻:CO₃²⁻ ratios from 0 to 1.62 and a pH of ∼10.9 were studied experimentally in batch reactors at 25 °C. The mineralogy, morphology and composition of the precipitates were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and microanalyses. The solids recovered after short reaction times (5 min to 1 h) consisted of a mixture of calcite and vaterite, with a S content that linearly correlates with the SO₄²⁻:CO₃²⁻ ratio in the aqueous solution. The solvent-mediated transformation of vaterite to calcite subsequently occurred. After 24 h of equilibration, calcite was the only phase present in the precipitate for aqueous solutions with SO₄²⁻:CO₃²⁻ ? 1. For SO₄²⁻:CO₃²⁻ > 1, vaterite persisted as a major phase for a longer time (>250 h for SO₄²⁻:CO₃²⁻ = 1.62). To study the role of sulfate in stabilizing vaterite, we performed a molecular simulation of the substitution of sulfate for carbonate groups into the crystal structure of vaterite, aragonite and calcite. The results obtained show that the incorporation of small amounts (<3 mole%) of sulfate is energetically favorable in the vaterite structure, unfavorable in calcite and very unfavorable in aragonite. The computer modeling provided thermodynamic information, which, combined with kinetic arguments, allowed us to put forward a plausible explanation for the observed crystallization behavior.     

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.