Shock-induced devolatilization of calcite

The amounts of CO₂ and CO evolved upon shock compression and decompression of calcite to 18 GPa (180 kbar) have been determined using a new gas phase shock recovery technique and gas source mass spectrometry. The data demonstrate that from ～0.03 to 0.3 mole percent of calcite is devolatilized at shock pressures significantly lower than those predicted (30 GPa) for the onset of volatilization by continuum thermodynamic theory and are in qualitative agreement with release adiabat data for calcite and aragonite. Carbon and oxygen isotope ratios in the shock-released CO₂ are the same as those in the unshocked (hydrothermal) calcite, demonstrating that the CO₂ comes from the calcite rather than other potential sources.     

Shock temperature in calcite (CaCO3) at 95-160 GPa

The temperatures induced in crystalline calcite (CaCO₃) upon planar shock compression (95-160 GPa) are reported from two-stage light gas gun experiments. Temperatures of 3300-5400 K are obtained by fitting six-channel optical pyrometer radiances in the 450-900 nm range to the Planck gray-body radiation law. Thermodynamic calculations demonstrate that these temperatures are some 400-1350 K lower than expected for vibronic excitations of the lattice with a 3R/mole-atom specific heat (R is gas constant). The temperature deficit along the Hugoniot is larger than that expected from only melting. In addition to melting, it appears likely that shock-induced decomposition of calcite occurs behind the shock front. We modeled disproportionation of calcite into CaO (solid) plus CO₂ (gas). For temperature calculations, specific heat at constant volume for 1 mole of CO₂ is taken to be 6.7R as compared to 9R in the solid state; whereas a mole of calcite and a mole of CaO have their solid state values 15R and 6R, respectively. Calculations suggest that the calcite decomposes to CaO and CO₂ at ∼110±10 GPa along the Hugoniot. Recent reanalysis of earlier VISAR measurements of particle velocity profiles [1] indicates that calcite shocked to 18 GPa undergoes disproportionation at much lower pressures upon isentropic expansion.     

The join grossularite-calcite through the system CaO—Al2O3—SiO2—CO2 at 30 kilobars: Crystallization range of silicates and carbonates on the liquidus

At 30 kbar, calcite melts congruently at 1615°C, and grossularite melts incongruently to liquid + gehlenite (tentative identification) at 1535°C. The assemblage calcite + grossularite melts at 1450°C to produce liquid + vapor, with piercing point at about 49 wt.% CaCO₃. Vapor phase is present in all hypersolidus phase fields except for those with less than about 7% CaCO₃ or 8% Ca₃Al₂Si₃O₁₂. These results, together with known liquidus data for CaO—SiO₂—CO₂ and inferred results for CaO—Al₂O₃—CO₂ and Al₂O₃—SiO₂—CO₂, permit construction of the position of the CO₂- saturated liquidus surface in the quaternary system, and estimation of the positions of liquidus field boundaries separating some of the primary crystallization fields on this surface. The field of calcite is separated from those for grossularite and quartz by a field boundary with about 50% dissolved CaCO₃. Crystallization paths of silicate liquids in the range Ca₂SiO₄—Ca₃Al₂Si₃O₁₂—SiO₂, with some dissolved CO₂, will terminate at a quaternary eutectic on this field boundary, with the precipitation of calcite together with grossularite and quartz, at a temperature below 1450°C. Addition of Al₂O₃ to CaO—SiO₂—CO₂ in amounts sufficient to stabilize garnet thus causes little change in the general liquidus pattern as far as carbonates and silicates are concerned. With addition of MgO, we anticipate that silicate liquids with dissolved CO₂ will also follow liquidus paths to fields for the precipitation of carbonates; we conclude that similar paths link kimberlite and some carnbonatite magmas.     

Relationship between13C and18O fractionation and changes in major element composition in a recent calcite-depositing spring — A model of chemical variations with inorganic CaCO3 precipitation

A theoretical model is derived in which isotopic fractionations can be calculated as a function of variations in dissolved carbonate species on CO₂ degassing and calcite precipitation. This model is tested by application to a calcite-depositing spring system near Westerhof, Germany. In agreement with the model,¹³C of the dissolved carbonate species changes systematically along the flow path. The difference in δ values between the upper and lower part of the stream is about 1‰. The¹³C content of the precipitated calcite is different from that expected from the theoretical partitioning. The isotopic composition of the solid CaCO₃ is similar to that of the dissolved carbonate, though in theory it should be isotopically heavier by about 2.4‰. The¹⁸O composition of dissolved carbonate and H₂O is constant along the stream. Calculated calcite-water temperatures differ by about +5°C from the observed temperatures demonstrating isotopic disequilibrium between the water and precipitated solid. This is attributed to kinetic effects during CaCO₃ deposition from a highly supersaturated solution, in which precipitation is faster than equilibration with respect to isotopes.Plant populations in the water have virtually no influence on CO₂ degassing, calcite saturation and isotopic fractionation. Measurements of P_CO2, S_C and¹³C within a diurnal cycle demonstrate that metabolic effects are below the detection limit in a system with a high supply-rate of dissolved carbonate species. The observed variations are due to differences in CO₂ degassing and calcite precipitation, caused by continuously changing hydrodynamic conditions and carbonate nucleation rates.     

Eutectic between wollastonite II and calcite contrasted with thermal barrier in MgO-SiO2-CO2 at 30 kilobars,with applications to kimberlite-carbonatite petrogenesis

In the join CaCO₃-CaSiO₃ at 30 kbars, calcite melts at 1615°C, wollastonite II at 1600°C, and a binary eutectic occurs at 1365°C with liquid composition 43 wt.% CaCO₃, 57 wt.% CaSiO₃. The eutectic liquid quenches to a glass with few quench crystals. In the join MgCO₃-MgSiO₃ at 30 kbars, magnesite melts at 1590°C, enstatite at 1837°C, and the fields for the primary crystallization of magnesite and enstatite are separated by a thermal barrier near 1900°C for the melting of forsterite in the presence of CO₂. Only about 10 wt.% MgSiO₃ dissolves in the carbonate liquid. These data, are considered together with incomplete results for joins CaMgSi₂O₆-CaMg(CO₃)₂, CaMgSi₂O₆-MgCO₃, CaMgSi₂O₆-CaCO₃, and other published data in the system CaO-MgO-SiO₂-CO₂. A thermal barrier separates the silicate and carbonate liquids in MgO-SiO₂-CO₂ but, in the quaternary system, silicate liquids with dissolved CO₂ can follow fractionation paths around the forsterite field to the fields for the primary crystallization of carbonates. This suggests that fractional crystallization of CO₂-bearing ultrabasic magma at 100 km depth can produce residual carbonatite magma.     

Shock-induced CO2 loss from CaCO3; implications for early planetary atmospheres

We report new results of shock recovery experiments on single crystal calcite. Recovered samples are subjected to thermogravimetric analysis. This yields the maximum amount of post-shock CO₂, the decarbonization interval, ΔT, and the energy of association (or vaporization), ΔEV, for the removal of remaining CO₂ in shock-loaded calcite. Comparison of post-shock CO₂ with that initially present determines shock-induced CO₂ loss as a function of shock pressure. Incipient to complete CO₂ loss occurs over a pressure range of 10to 70GPa. The latter pressure should be considered a lower bound. Comparable to results on hydrous minerals, ΔT and ΔEV decrease systematically with increasing shock pressure. This indicates that shock loading leads to both the removal of structural volatiles and weakening of bonds between the volatile species and remainder of the crystal lattice.Optical and scanning electron microscopy (SEM) reveal structural changes, which are related to the shock-loading. Comparable to previous findings on shocked antigorite is the occurrence of dark, diffuse areas, which can be resolved as highly vesicular areas as observed with a scanning electron microscope. These areas are interpreted as representing quenched partial melts, into which shock-released CO₂ has been injected.The experimental results are used to place bonds on models of impact production of CO₂ during accretion of the terrestrial planets.     

Carbon isotopic compositions of Recent planktonic foraminifera of the Indian Ocean

Carbon and oxygen isotopic determinations have been made of 29 species of Recent Indian Ocean planktonic foraminifera. Fourteen core-top samples were used and as many as 18 species were chosen from a single core-top sample. The δ¹³C of the foraminifera was compared with that of total dissolved CO₂ (ΣCO₂) and of calcite precipitated in isotopic equilibrium with ΣCO₂. The foraminiferal calcite is always at least 1.2‰ less than the value estimated for equilibrium calcite. This carbon isotopic disequilibrium suggests the partial utilization of¹³C-depleted metabolic CO₂. The calcite tests of several species, however, have δ¹³C values which are similar to the δ¹³C of ΣCO₂ in seawater. This relationship suggests that important paleohydrographic information may be obtained from carbon isotope records based on analyses of several foraminiferal species from single deep-sea sediment samples.     

High-pressure phases of CaCO3: Crystal structure prediction and experiment

Post-aragonite phase of CaCO₃, experimentally known to be stable above 40 GPa [S. Ono, T. Kikegawa, Y. Ohishi, J. Tsuchiya, Post-aragonite phase transformation in CaCO₃ at 40 GPa, Am. Mineral. 90 (2005) 667–671], is believed to be a major carbon-containing mineral in the Earth's mantle. Crystal structure of this mineral phase could not be solved using experimental data or traditional theoretical simulation methods and remained a controversial issue. Using a combination of advanced ab initio simulation techniques and high-pressure experiment, we have been able to determine the crystal structure of CaCO₃ post-aragonite. Here, we performed simulations with the USPEX code [C.W. Glass, A.R. Oganov, and N. Hansen, (in preparation). USPEX: a universal structure prediction program], which is based on an evolutionary algorithm using ab initio free energy as the fitness function. This novel methodology for crystal structure prediction, which uses only the chemical composition as input, is described in detail. For CaCO₃, we identify a number of energetically competitive structures, the most stable of which closely matches the experimental powder diffraction pattern and, in agreement with experiment, becomes more stable than aragonite above 42 GPa. This structure belongs to a new structure type, which is also adopted by the high-pressure post-aragonite phases of SrCO₃ and BaCO₃. It has 2 formula units in the orthorhombic unit cell (space group Pmmn) and contains triangular CO₃²⁻ ions and Ca²⁺ ions in the 12-fold coordination. Above 137 GPa, a pyroxene-type structure (space group C222₁) with chains of CO₄⁴⁻ tetrahedra becomes more stable than post-aragonite. For MgCO₃, this structure becomes more stable than magnesite above 106 GPa and is a good candidate structure for MgCO₃ post-magnesite.     

Biomass effects on stalagmite growth and isotope ratios: A 20th century analogue from Wiltshire, England

Increases in calcite deposition rates combined with decreases in δ¹³C and δ¹⁸O in three modern stalagmites from Brown's Folly Mine, Wiltshire, England, are correlative with a well-documented re-vegetation above the mine. Increased soil P_CO2 resulted in greater amounts of dissolved CaCO₃ in the drip waters, which consequently increased annual calcite deposition rates. The absence of deposition prior to 1916 (28 years after the mine was closed) indicates that vegetation had not yet sufficiently developed to allow higher P_CO2 values to form in the soil. Lower δ¹³C values through time may reflect the increased input of isotopically light biogenic carbon to the total dissolved inorganic carbon (DIC). δ¹⁸O decreased synchronously with δ¹³C, reflecting the increased importance of isotopically light winter recharge due to greater biomass-induced summer evapotranspiration. This is the first empirical demonstration that vegetation density can control stalagmite growth rates, δ¹³C, and δ¹⁸O, contributing critical insights into the interpretation of these climate proxies in ancient stalagmites.     

Dynamischer Zinkaustausch an umweltrelevanten anorganischen Festphasen

The fixation of slightly soluble substances on inert carriers offers the possibility to examine the exchange of heavy metals at these phases under dynamic conditions. Investigations are presented for the exchange of Zinc under various conditions (pH, different concentrations of other cations such as Na⁺ and Ca²⁺ or of NTA as a chelating agent) on fixed MnO₂-hydrate, Fe(OH₃), CaCO₃ and a natural clay-slate. Batch-experiments showed that all phases are able to sorb Zinc with MnO₂-hydrate as the best sorbent for this metal (highest sorption constant and capacity). Column desorption experiments demonstrate that a decrease of the pH of the aqueous phase or an addition of NTA remobilise Zinc from MnO₂-hydrate, Fe(OH)₃, CaCO₃ and also from the clay-slate. The same effect of releasing sorbed metal (with exception of the CaCO₃-phase) show Na⁺ or Ca²⁺ containing solutions. Therefore Zinc is bonded under natural conditions on the oxihydrates and the clay-slate in a labile, ion-exchangeable form in contrast to CaCO₃, on which Zinc is sorbed probably as the carbonate.     

Elucidating geochemical response of shallow heterogeneous aquifers to CO2 leakage using high-performance computing: Implications for monitoring of CO2 sequestration

Predicting and quantifying impacts of potential carbon dioxide (CO₂) leakage into shallow aquifers that overlie geologic CO₂ storage formations is an important part of developing reliable carbon storage techniques. Leakage of CO₂ through fractures, faults or faulty wellbores can reduce groundwater pH, inducing geochemical reactions that release solutes into the groundwater and pose a risk of degrading groundwater quality. In order to help quantify this risk, predictions of metal concentrations are needed during geologic storage of CO₂. Here, we present regional-scale reactive transport simulations, at relatively fine-scale, of CO₂ leakage into shallow aquifers run on the PFLOTRAN platform using high-performance computing. Multiple realizations of heterogeneous permeability distributions were generated using standard geostatistical methods. Increased statistical anisotropy of the permeability field resulted in more lateral and vertical spreading of the plume of impacted water, leading to increased Pb²⁺ (lead) concentrations and lower pH at a well down gradient of the CO₂ leak. Pb²⁺ concentrations were higher in simulations where calcite was the source of Pb²⁺ compared to galena. The low solubility of galena effectively buffered the Pb²⁺ concentrations as galena reached saturation under reducing conditions along the flow path. In all cases, Pb²⁺ concentrations remained below the maximum contaminant level set by the EPA. Results from this study, compared to natural variability observed in aquifers, suggest that bicarbonate (HCO₃⁻) concentrations may be a better geochemical indicator of a CO₂ leak under the conditions simulated here.     

Vadose CO2 gas drives dissolution at water tables in eogenetic karst aquifers more than mixing dissolution

Most models of cave formation in limestone that remains near its depositional environment and has not been deeply buried (i.e. eogenetic limestone) invoke dissolution from mixing of waters that have different ionic strengths or have equilibrated with calcite at different _pCO₂ values. In eogenetic karst aquifers lacking saline water, mixing of vadose and phreatic waters is thought to form caves. We show here calcite dissolution in a cave in eogenetic limestone occurred due to increases in vadose CO₂ gas concentrations and subsequent dissolution of CO₂ into groundwater, not by mixing dissolution. We collected high‐resolution time series measurements (1 year) of specific conductivity (SpC), temperature, meteorological data, and synoptic water chemical composition from a water table cave in central Florida (Briar Cave). We found SpC, _pCO₂ and calcite undersaturation increased through late summer, when Briar Cave experienced little ventilation by outside air, and decreased through winter, when increased ventilation lowered cave CO_2(g) concentrations. We hypothesize dissolution occurred when water flowed from aquifer regions with low _pCO₂ into the cave, which had elevated _pCO₂. Elevated _pCO₂ would be promoted by fractures connecting the soil to the water table. Simple geochemical models demonstrate that changes in _pCO₂ of less than 1% along flow paths are an order of magnitude more efficient at dissolving limestone than mixing of vadose and phreatic water. We conclude that spatially or temporally variable vadose CO_2(g) concentrations are responsible for cave formation because mixing is too slow to generate observed cave sizes in the time available for formation. While this study emphasized dissolution, gas exchange between the atmosphere and karst aquifer vadose zones that is facilitated by conduits likely exerts important controls on other geochemical processes in limestone critical zones by transporting oxygen deep into vadose zones, creating redox boundaries that would not exist in the absence of caves. Copyright © 2014 John Wiley & Sons, Ltd.     

Very high-frequency and seasonal cave atmosphere PCO2 variability: Implications for stalagmite growth and oxygen isotope-based paleoclimate records

Cave air P_CO2 at two Irish sites varied dramatically on daily to seasonal timescales, potentially affecting the timing of calcite deposition and consequently climate proxy records derived from stalagmites collected at the same sites. Temperature-dependent biochemical processes in the soil control CO₂ production, resulting in high summer P_CO2 values and low winter values at both sites. Large Large-amplitude, high-frequency variations superimposed on this seasonal cycle reflect cave air circulation. Here we model stalagmite growth rates, which are controlled partly by CO₂ degassing rates from drip water, by considering both the seasonal and high-frequency cave air P_CO2 variations. Modeled hourly growth rates for stalagmite CC-Bil from Crag Cave in SW Ireland reach maxima in late December (0.063 μm h^− 1) and minima in late June/early July (0.033 μm h^− 1). For well-mixed ‘diffuse flow’ cave drips such as those that feed CC-Bil, high summer cave air P_CO2 depresses summer calcite deposition, while low winter P_CO2 promotes degassing and enhances deposition rates. In stalagmites fed by well-mixed drips lacking seasonal variations in δ¹⁸O, integrated annual stalagmite calcite δ¹⁸O is unaffected; however, seasonality in cave air P_CO2 may influence non-conservative geochemical climate proxies (e.g., δ¹³C, Sr/Ca). Stalagmites fed by ‘seasonal’ drips whose hydrochemical properties vary in response to seasonality may have higher growth rates in summer because soil air P_CO2 may increase relative to cave air P_CO2 due to higher soil temperatures. This in turn may bias stalagmite calcite δ¹⁸O records towards isotopically heavier summer drip water δ¹⁸O values, resulting in elevated calcite δ¹⁸O values compared to the ‘equilibrium’ values predicted by calcite–water isotope fractionation equations. Interpretations of stalagmite-based paleoclimate proxies should therefore consider the consequences of cave air P_CO2 variability and the resulting intra-annual variability in calcite deposition rates.     

Diagenetic transformations and silcrete–calcrete intergrade duricrust formation in palaeo‐estuary sediments

The Boteti palaeo‐estuary in northern Botswana is located where the endoreic Boteti river, an overflow from the regional Okavango river system, enters the Makgadikgadi pans. The present work considers diagenetic silica and calcium carbonate dominated transformations. The aims are to help identify precursor conditions for the origin of microcrystalline silcrete–calcrete intergrade deposits while developing insight into pene‐contemporaneous silica and calcite matrix formation. General precursor conditions require the presence of cyclical endoreic freshwater inflow into a saline pan. The pan should be deep enough to sustain a permanent watertable under climatic conditions sufficient to cause carbonate fractionation within the groundwater. Freshwater inflow into a saline pan drives the geochemistry of the system (from freshwater to saline, from neutral to high pH). The geochemistry is controlled by the periodicity of inflow relative to salinity levels of phreatic groundwater in the receptor saline pan. The source of most silica and localized CaCO₃ is derived from the dissolution and precipitation of micro‐fossils, while more general CaCO₃ enrichment stems from saline pan based carbonate fractionation. Diagenetic change leads to colloidal then more consolidated bSiO₂/CaO aggregate formation (amorphous silica) followed by transformations into opaline silica over time. Irregular zones of siliceous sediment forming in otherwise calcareous deposits may relate to the irregular occurrence of biogenic silica in the source sediments, inferring a source for local silica mobilization in intergrade deposits. The distribution of calcareous micro‐fossils may have a similar converse effect. Diagenetic evidence from an intergrade deposit with a low SiO₂/CaO ratio suggests that transformation occurred more into the pan, while an intergrade deposit with a high SiO₂/CaO ratio more likely formed closer to a land margin and was frequently inundated by freshwater. Pene‐contemporaneous silcrete–calcrete intergrade formation under the above conditions may take place where dissolved silica crystallizes out in the vicinity of calcite crystals due to local decreases in pH. The continuing consolidation of bSiO₂/CaO aggregates may be facilitated by the presence of increasing amounts of calcite. It appears that CaCO₃ may act as a catalyst leading to pene‐contemporaneous bSiO₂/CaO aggregate formation. However the processes involved require further work. Copyright © 2013 John Wiley & Sons, Ltd.     

Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2 concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2 ]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.     

Biosilicium (BSi) in Sedimenten Mecklenburger Seen (Deutschland) und das Calciumcarbonat-Biosilicium-Verhältnis als Trophie- und Wasserstandsindikator Biogenic Silica (BSi) in Sediments of the Mecklenburgian Lake District (Germany) and the Calcite-Silica-Relation as Indicator for Trophy and Water Level

The BSi content has been investigated in the surface sediments of lakes of different trophic state in the Mecklenburgian Lake District. The BSi content differs between 1 to 1000 mg BSi/g dry matter. High values were found in deep eutrophic lakes. Litoral sediments and shallow eutrophic lakes have lower contents. BSi content was found to be correlated with lake morphometry, depth, trophic level, sediment composition and especially with calcite. With the CaCO₃/BSi-value, 3 groups of lakes can be characterized:

• CaCO₃/BSi = 0 oligotrophic and dystrophic lakes
• CaCO₃/BSi ≤ 10 mesotrophic and eutrophic deep lakes
• CaCO₃/BSi ≤ 10 eutrophic shallow lakes

The results from the recent sediments have been compared with those from older sediments. Using the CaCO₃/BSi-value, climatic change, trophic state, and sea level can be detected.     

Chemical geothermometry and fluid–mineral equilibria for the Ömer–Gecek thermal waters, Afyon area, Turkey

Thermal waters of the Ömer–Gecek geothermal field, Turkey, with temperatures ranging from 32 to 92°C vary in chemical composition and TDS contents. They are generally enriched in Na–Cl–HCO₃ and suggest deep water circulation. Silica and cation geothermometers applied to the Ömer–Gecek thermal waters yield reservoir temperatures of 75–155°C. The enthalpy–chloride mixing model, which approximates a reservoir temperature of 125°C for the Ömer–Gecek field, accounts for the diversity in the chemical composition and temperature of the waters by a combination of processes including boiling and conductive cooling of deep thermal water and mixing of the deep thermal water with cold water. It is also determined that the solubility of silica in most of the waters is controlled by the chalcedony phase. Equilibrium states of the Ömer–Gecek thermal waters studied by means of the Na–K–Mg triangular diagram, Na–K–Mg–Ca diagram, K–Mg–Ca geoindicator diagram, activity diagrams in the systems composed of Na₂O–CaO–K₂O–Al₂O₃–SiO₂–CO₂–H₂O phases, log SI diagrams, and finally the alteration mineralogy indicate that most of the spring and low-temperature well waters in the area can be classified as shallow or mixed waters which are likely to be equilibrated with calcite, chalcedony and kaolinite at predicted temperature ranges similar to those calculated from the chemical geothermometers. It was also observed that mineral equilibrium in the Ömer–Gecek waters is largely controlled by CO₂ concentrations.     

The importance of ocean temperature to global biogeochemistry

Variations in the mean temperature of the ocean, on time scales from millennial to millions of years, in the past and projected for the future, are large enough to impact the geochemistry of the carbon, oxygen, and methane geochemical systems. In each system, the time scale of the temperature perturbation is key. On time frames of 1-100 ky, atmospheric CO₂ is controlled by the ocean. CO₂ temperature-dependent solubility and greenhouse forcing combine to create an amplifying feedback with ocean temperature; the CaCO₃ cycle increases this effect somewhat on time scales longer than ∼5-10 ky. The CO₂/T feedback can be seen in the climate record from Vostok, and a model including the temperature feedback predicts that 10% of the fossil fuel CO₂ will reside in the atmosphere for longer than 100 ky. Timing is important for oxygen, as well; the atmosphere controls the ocean on short time scales, but ocean anoxia controls atmospheric pO₂ on million-year time scales and longer. Warming the ocean to Cretaceous temperatures might eventually increase pO₂ by approximately 25%, in the absence of other perturbations. The response of methane clathrate to climate change in the coming century will probably be small, but on longer time scales of 1-10 ky, there may be a positive feedback with ocean temperature, amplifying the long-term climate impact of anthropogenic CO₂ release.     

Measurement of Natural Losses of LNAPL Using CO2 Traps

Efflux of CO₂ above releases of petroleum light nonaqueous phase liquids (LNAPLs) has emerged as a critical parameter for resolving natural losses of LNAPLs and managing LNAPL sites. Current approaches for resolving CO₂ efflux include gradient, flux chamber, and mass balance methods. Herein a new method for measuring CO₂ efflux above LNAPL bodies, referred to as CO₂ traps, is introduced. CO₂ traps involve an upper and a lower solid phase sorbent elements that convert CO₂ gas into solid phase carbonates. The sorbent is placed in an open vertical section of 10 cm ID polyvinyl chloride (PVC) pipe located at grade. The lower sorbent element captures CO₂ released from the subsurface via diffusion and advection. The upper sorbent element prevents atmospheric CO₂ from reaching the lower sorbent element. CO₂ traps provide integral measurement of CO₂ efflux based over the period of deployment, typically 2 to 4 weeks. Favorable attributes of CO₂ traps include simplicity, generation of integral (time averaged) measurement, and a simple means of capturing CO₂ for carbon isotope analysis. Results from open and closed laboratory experiments indicate that CO₂ traps quantitatively capture CO₂. Results from the deployment of 23 CO₂ traps at a former refinery indicate natural loss rates of LNAPL (measured in the fall, likely concurrent with high soil temperatures and consequently high degradation rates) ranging from 13,400 to 130,000 liters per hectare per year (L/Ha/year). A set of field triplicates indicates a coefficient of variation of 18% (resulting from local spatial variations and issues with measurement accuracy).     

A method for incorporating equilibrium chemical reactions into multiphase flow models for CO2 storage

CO₂ injection and storage in deep saline aquifers involves many coupled processes, including multiphase flow, heat and mass transport, rock deformation and mineral precipitation and dissolution. Coupling is especially critical in carbonate aquifers, where minerals will tend to dissolve in response to the dissolution of CO₂ into the brine. The resulting neutralization will drive further dissolution of both CO₂ and calcite. This suggests that large cavities may be formed and that proper simulation may require full coupling of reactive transport and multiphase flow. We show that solving the latter may suffice whenever two requirements are met: (1) all reactions can be assumed to occur in equilibrium and (2) the chemical system can be calculated as a function of the state variables of the multiphase flow model (i.e., liquid and gas pressure, and temperature). We redefine the components of multiphase flow codes (traditionally, water and CO₂), so that they are conservative for all reactions of the chemical system. This requires modifying the traditional constitutive relationships of the multiphase flow codes, but yields the concentrations of all species and all reaction rates by simply performing speciation and mass balance calculations at the end of each time step. We applied this method to the H₂O–CO₂–Na–Cl–CaCO₃ system, so as to model CO₂ injection into a carbonate aquifer containing brine. Results were very similar to those obtained with traditional formulations, which implies that full coupling of reactive transport and multi-phase flow is not really needed for this kind of systems, but the resulting simplifications may make it advisable even for cases where the above requirements are not met. Regarding the behavior of carbonate rocks, we find that porosity development near the injection well is small because of the low solubility of calcite. Moreover, dissolution concentrates at the front of the advancing CO₂ plume because the brine below the plume tends to reach high CO₂ concentrations quite rapidly. We conclude that carbonate dissolution needs not to be feared.