Relationship between Se/S and sulfur isotope ratios of hydrothermal sulfide minerals

The pH and f_{O 2} dependences of the [Se^2–]/[S^2–] ratio in chloride solutions at 100°, 200° and 300°C are predicted thermodynamically. Under the high f_{O 2} conditions where sulfate species are dominant in solution, the [Se^2–]/[S^2–] ratio always increases with increasing pH and/or f_{O 2}. Under the low f_{O 2} conditions where sulfide species are dominant in solution, the pH and f_{O 2} dependences of the [Se^2–]/[S^2–] ratio are seriously affected by the presence of native selenium. With native selenium present, the [Se^2–]/[S^2–] ratio decreases with increasing f_{O 2}, but almost independent of pH in geologically important pH regions. When native selenium is absent, the [Se^2–]/[S^2–] ratio is solely a function of pH and independent of f_{O 2}. Combining the above with the pH and f_{O 2} dependences of ³⁴S value of aqueous sulfur species, we discuss the possible influences of the pH and f_{O 2} of ore-forming solutions on the relationship between the Se/S ratio and ³⁴S value of hydrothermal sulfide minerals. The results are applied to some Japanese sulfide ore deposits.     

Mechanism of the water and carbon dioxide solubility in oxides and silicates and the role of O−

The dissolution of water does not stop at the OH^– stage but may proceed further towards H₂ plus O^– formation. The discovery of atomic carbon dissolved in minerals suggests that, if CO₂ enters oxides and silicates at high pressures and temperatures, not only [CO₃]^2– ions but also [CO ₄ ^. ]^4– complexes are formed via a charge transfer which produces O^– and essentially zero-valent, atomic carbon. Under P —T-conditions of the mantle, where the solubility for water and CO₂ is high, the silicate phases formed may therefore consist to a large volume fraction of O^– ions which are much smaller than O^2–ions and strongly cova-lently bonding. The implications for the crystal chemistry of high pressure phases, for the petrology of mantle rocks are outlined.     

Processes controlling precipitation of carbonate cement and dissolution of silica in reef and near-reef settings

Carbonate cementation in the surface layer of reefs and beachrock eliminates porosity and partially replaces detrital quartz grains. The uptake and release of CO₂ by photosynthesis and respiration in reef communities cause a shift in the carbonate buffer system of seawater. Field studies and experimentation simulating the natural settings show minimum values of CO₂ (1.9 mmoles 1^?1) and HCO₃^? (2.4 meq 1^?1) in association with maximum values of pH (9.8) and O₂ (> 100% oxygen saturation) in waters covering corals and algae prior to sunset. The converse is true for these variables prior to sunrise, when minimum values of pH (7.6) and O₂ (<66% oxygen saturation) occur with maximum values of CO₂ (2.7 mmoles 1^?1) and HCO₃^? (2.7 meq 1^?1). Experimental tanks containing plain seawater showed almost no diurnal variability in pH (a constant 7.5–7.6) or O₂ (80–90% oxygen saturation) measurements. Seawater adjacent to reef biomass, with elevated pH and supersaturated with calcium carbonate, is periodically pumped into the underlying reef and beach sediments due to pressure-buildups between the reef framework or algal zones and open waters. Carbonate precipitation and quartz dissolution follow. As the system equilibrates, pH values progressively decrease.     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.     

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).     

Evolution of the chemistry of Fe bearing waters during CO2 degassing

The rates of Fe(II) oxidation and precipitation from groundwater are highly pH dependent. Elevated levels of dissolved CO₂ can depress pH and cause difficulty in removing dissolved Fe and associated metals during treatment of ferruginous water. This paper demonstrates interdependent changes in pH, dissolved inorganic C species, and Fe(II) oxidation rates that occur as a result of the removal (degassing) of CO₂ during aeration of waters discharged from abandoned coal mines. The results of field monitoring of aeration cascades at a treatment facility as well as batchwise aeration experiments conducted using net alkaline and net acidic waters in the UK are combined with geochemical modelling to demonstrate the spatial and temporal evolution of the discharge water chemistry. The aeration cascades removed approximately 67% of the dissolved CO₂ initially present but varying the design did not affect the concentration of Fe(II) leaving the treatment ponds. Continued removal of the residual CO₂ by mechanical aeration increased pH by as much as 2 units and resulted in large increases in the rates of Fe(II) oxidation and precipitation. Effective exsolution of CO₂ led to a reduction in the required lime dose for removal of remaining Fe(II), a very important factor with regard to increasing the sustainability of treatment practices. An important ancillary finding for passive treatment is that varying the design of the cascades had little impact on the rate of CO₂ removal at the flow rates measured.     

Heavy metal migration at a landfill site,Sarnia, Ontario,Canada—I. Thermodynamic assessment and chemical interpretations

The transition metals Fe, Cu, Zn and Pb have diffused only 10–20 cm into the clay barrier at the Confederation Road landfill compared to 130 cm for porewater chloride. Other major dissolved species, including the alkali and alkaline earth metals, have also diffused out of waste landfill and into clay subsoils more rapidly than the metals. Redox potentials, E_h, indicate strongly reducing conditions (E_h= − 130 mV) in the clayey soil at the subsoil/waste interface and increase to +50 mV at a depth of 45 cm below the interface. pH values are close to 8 within the subsoil but the slightly lower values (7.8–8) near the interface may result from production of organic acids during degradation of the wastes. Thermodynamic analysis of subsoil pore waters indicates that Fe, Cu, Zn and Pb exist primarily as metal-hydroxy complexes of the forms [MeOH]⁺ and [Me(OH)₂]⁰, although a complex of [PbCl]⁺ may be significant, but not predominant. The analysis also demonstrates that the dissolved transition metal concentrations of the subsoil pore waters are controlled at carbonate mineral saturation levels, whereas Fe concentrations in leachate solutions associated with the wastes are controlled at FeS₂ saturation levels.Thermodynamic calculations and E_h-pH diagrams suggest that Fe(OH)₂, Zn(OH)₂ and Pb(OH)₂ are not stable phases in the solids of the subsoil. This means that observed “hydroxide” phases reported in the selective dissolution analysis by Yanful and Quigley (1986) have to be re-evaluated.     

GEOCARBSULF: A combined model for Phanerozoic atmospheric O2 and CO2

A model for the combined long-term cycles of carbon and sulfur has been constructed which combines all the factors modifying weathering and degassing of the GEOCARB III model [Berner R.A., Kothavala Z., 2001. GEOCARB III: a revised model of atmospheric CO₂ over Phanerozoic time. Am. J. Sci. 301, 182-204] for CO₂ with rapid recycling and oxygen dependent carbon and sulfur isotope fractionation of an isotope mass balance model for O₂ [Berner R.A., 2001. Modeling atmospheric O₂ over Phanerozoic time. Geochim. Cosmochim. Acta65, 685-694]. New isotopic data for both carbon and sulfur are used and new feedbacks are created by combining the models. Sensitivity analysis is done by determining (1) the effect on weathering rates of using rapid recycling (rapid recycling treats carbon and sulfur weathering in terms of young rapidly weathering rocks and older more slowly weathering rocks); (2) the effect on O₂ of using different initial starting conditions; (3) the effect on O₂ of using different data for carbon isotope fractionation during photosynthesis and alternative values of oceanic δ¹³C for the past 200 million years; (4) the effect on sulfur isotope fractionation and on O₂ of varying the size of O₂ feedback during sedimentary pyrite formation; (5) the effect on O₂ of varying the dependence of organic matter and pyrite weathering on tectonic uplift plus erosion, and the degree of exposure of coastal lands by sea level change; (6) the effect on CO₂ of adding the variability of volcanic rock weathering over time [Berner, R.A., 2006. Inclusion of the weathering of volcanic rocks in the GEOCARBSULF model. Am. J. Sci.306 (in press)]. Results show a similar trend of atmospheric CO₂ over the Phanerozoic to the results of GEOCARB III, but with some differences during the early Paleozoic and, for variable volcanic rock weathering, lower CO₂ values during the Mesozoic. Atmospheric oxygen shows a major broad late Paleozoic peak with a maximum value of about 30% O₂ in the Permian, a secondary less-broad peak centered near the Silurian/Devonian boundary, variation between 15% and 20% O₂ during the Cambrian and Ordovician, a very sharp drop from 30% to 15% O₂ at the Permo-Triassic boundary, and a more-or less continuous rise in O₂ from the late Triassic to the present.     

Daytime deposition and nighttime dissolution of calcium carbonate controlled by submerged plants in a karst spring-fed pool: insights from high time-resolution monitoring of physico-chemistry of water

Water temperature, dissolved oxygen (DO), pH, and specific conductivity (spc) were measured in a time interval of 15 min in a karst spring and the spring-fed pool with flourishing submerged plants in Guilin, SW China under dry weather for periods of 2 days. Measurements allowed calculation of calcium and bicarbonate concentrations ([Ca²⁺] and [HCO₃ ⁻]), and thus CO₂ partial pressure ( ) and saturation index of calcite (SIc). Results show that there were not any diurnal variations in the physico-chemical parameters of the water for the spring. However, during daytime periods, pool water decreased to far less than the spring water in a few hours, pH and SIc increased to greater than the spring, and [Ca²⁺] and [HCO₃ ⁻] decreased to less than the spring. During nighttime periods, pool water returned to or even increased to greater than the spring, pH and SIc decreased to less than the spring, and [Ca²⁺] and [HCO₃ ⁻] increased to greater than the spring. The decrease in [Ca²⁺] and [HCO₃ ⁻] to less than the spring during daytime periods implies daytime deposition of calcium carbonate, while the increase in [Ca²⁺] and [HCO₃ ⁻] to greater than the spring during nighttime periods implies nighttime dissolution of calcium carbonate. The direction of the observed changes depended essentially on the illumination, indicating that daytime photosynthetic and nighttime respiratory activities in the pool aquatic plant ecosystem, which were further evidenced by the increase and decrease in DO during daytime and nighttime periods respectively, were the main processes involved. The large variations of the components of the carbonate system imply considerable changes of the capacities of CO₂ and O₂ in water. The finding has implications for water sampling strategy in slow-flowing karst streams and other similar environments with stagnant water bodies such as estuaries, lakes, reservoirs, and wetlands, where aquatic plant ecosystem may flourish.     

The role of “excess” CO2 in the formation of trona deposits

The prevailing theory for the formation of trona [Na₃(CO₃)(HCO₃) · 2(H₂O)] relies on evaporative concentration of water produced by silicate hydrolysis of volcanic rock or volcaniclastic sediments. Given the abundance of closed drainage basins dominated by volcanics, it is puzzling that there are so few trona deposits and present-day lakes that would yield dominantly Na–CO₃ minerals upon evaporation. Groundwater in the San Bernardino Basin (southeastern Arizona, USA and northeastern Sonora, Mexico) would yield mainly Na–CO₃ minerals upon evaporation, but waters in the surrounding basins would not. Analysis of the chemical evolution of this groundwater shows that the critical difference from the surrounding basins is not lithology, but the injection of magmatic CO₂. Many major deposits of trona and Na–CO₃-type lakes appear to have had “excess” CO₂ input, either from magmatic sources or from the decay of organic matter. It is proposed that, along with the presence of volcanics, addition of “excess” CO₂ is an important pre-condition for the formation of trona deposits.     

Diurnal variations of pCO2 in relation to environmental factors in the cascade reservoirs along the Wujiang River, China

We have investigated the diurnal variations of the pCO2 and related environmental factors in the cascade reservoirs with different trophic levels along Wujiang River. In surface water the pCO2 was 357±11 μatm in Hong-jiadu Reservoir, 338±48 μatm in Dongfeng Reservoir, 682±303 μatm in Wujiangdu Reservoir, and 1677±429 μatm in Liuguang, respectively. The results indicated that these cascade reservoirs had much lower pCO2 values in surface water than river did, and hypereutrophic reservoir showed larger diurnal variations of pCO2 than meso-eutrophic reservoir. In water column, pCO2 tended to increase with the depth. Phytoplankton and the environmental factors such as temperature and pH had different influences on pCO2 diurnal variations due to different trophic levels, and the effect of phytoplankton on pCO2 variation increased with the increase of trophic level in these reservoirs.     

Microenvironmental controls on mineralogy and habit of CaCO3 precipitates: an example from an active travertine system

Analysis of water and associated carbonate precipitates from a small, warm-spring travertine system in SW Colorado, USA, provide an example of the: (i) great variability of the geochemical parameters within these dynamic systems, and (ii) significance of the microenvironment in controlling mineralogy and morphology of carbonate precipitates. Waters emerged from the springs highly charged in CO₂, with an initial p_CO2 of 1.2 × 10⁵ Pa. Degassing of the CO₂ from the waters decreased the pH from 6.1 to 8.0, resulting in an increase of 8%‰ in δ¹³C values downflow in the total CO₂ in solution and an increase in the I_SAT from 2.1 to as high as 63 times supersaturation with respect to calcite. Due to changes in the stable isotopic composition of the waters downflow as well as changes in the degree of supersaturation, stable isotopic analyses range greatly from locale to locale within this small system. Near the spring vents, at relatively low I_SAT levels, well-developed rhombohedra of calcite formed as biotically induced precipitates around diatom stalks and other algae as well as abiotic crusts. In contrast, near the distal end of the system, very high I_SAT levels were reached and resulted in the precipitation of skeletal-dendritic crystals of calcite on copper substrates, floating rafts of laterally linked hemispheres of aragonite crystals, and bimineralic carbonate-encrusted bubbles. Microenvironmental parameters control the mineralogy and habit of these precipitates.     

A physicochemical framework for interpreting the biological calcification response to CO2-induced ocean acidification

A generalized physicochemical model of the response of marine organisms’ calcifying fluids to CO₂-induced ocean acidification is proposed. The model is based upon the hypothesis that some marine calcifiers induce calcification by elevating pH, and thus Ω_A, of their calcifying fluid by removing protons (H⁺). The model is explored through two end-member scenarios: one in which a fixed number of H⁺ is removed from the calcifying fluid, regardless of atmospheric pCO₂, and another in which a fixed external-internal H⁺ ratio ([H⁺]_E/[H⁺]_I) is maintained. The model is able to generate the full range of calcification response patterns observed in prior ocean acidification experiments and is consistent with the assertion that organisms’ calcification response to ocean acidification is more negative for marine calcifiers that exert weaker control over their calcifying fluid pH. The model is empirically evaluated for the temperate scleractinian coral Astrangia poculata with in situ pH microelectrode measurements of the coral’s calcifying fluid under control and acidified conditions. These measurements reveal that (1) the pH of the coral’s calcifying fluid is substantially elevated relative to its external seawater under both control and acidified conditions, (2) the coral’s [H⁺]_E/[H⁺]_I is approximately the same under control and acidified conditions, and (3) the coral removes fewer H⁺ from its calcifying fluid under acidified conditions than under control conditions. Thus, the carbonate system dynamics of A. poculata’s calcifying fluid appear to be most consistent with the fixed [H⁺]_E/[H⁺]_I end-member scenario. Similar microelectrode experiments performed on additional taxa are required to assess the model’s general applicability.     

Brucite [Mg(OH2)] carbonation in wet supercritical CO2: An in situ high pressure X-ray diffraction study

Understanding mechanisms and kinetics of mineral carbonation reactions relevant to sequestering carbon dioxide as a supercritical fluid (scCO₂) in geologic formations is crucial to accurately predicting long-term storage risks. Most attention so far has been focused on reactions occurring between silicate minerals and rocks in the aqueous dominated CO₂-bearing fluid. However, water-bearing scCO₂ also comprises a reactive fluid, and in this situation mineral carbonation mechanisms are poorly understood. Using in situ high-pressure X-ray diffraction, the carbonation of brucite [Mg(OH)₂] in wet scCO₂ was examined at pressure (82 bar) as a function of water concentration and temperature (50 and 75 °C). Exposing brucite to anhydrous scCO₂ at either temperature resulted in little or no detectable reaction over three days. However, addition of trace amounts of water resulted in partial carbonation of brucite into nesquehonite [MgCO₃·3H₂O] within a few hours at 50 °C. By increasing water content to well above the saturation level of the scCO₂, complete conversion of brucite into nesquehonite was observed. Tests conducted at 75 °C resulted in the conversion of brucite into magnesite [MgCO₃] instead, apparently through an intermediate nesquehonite step. Raman spectroscopy applied to brucite reacted with ¹⁸O-labeled water in scCO₂ show it was incorporated into carbonate at a relatively high concentration. This supports a carbonation mechanism with at least one step involving a direct reaction between the mineral and water molecules without mediation by a condensed aqueous layer.     

Oxidation of iron (II) nanomolar with H2O2 in seawater

The oxidation of Fe(II) with H₂O₂ at nanomolar levels in seawater have been studied using an UV-Vis spectrophotometric system equipped with a long liquid waveguide capillary flow cell. The effect of pH (6.5 to 8.2), H₂O₂ (7.2 × 10⁻⁸ M to 5.2 × 10⁻⁷ M), HCO₃⁻ (2.05 mM to 4.05 mM) and Fe(II) (5 nM to 500 nM) as a function of temperature (3 to 35 °C) on the oxidation of Fe(II) are presented. The oxidation rate is linearly related to the pH with a slope of 0.89 ± 0.01 independent of the concentration of HCO₃⁻. A kinetic model for the reaction has been developed to consider the interactions of Fe(II) with the major ions in seawater. The model has been used to examine the effect of pH, concentrations of Fe(II), H₂O₂ and HCO₃⁻ as a function of temperature. FeOH⁺ is the most important contributing species to the overall rate of oxidation from pH 6 to pH 8. At a pH higher than 8, the Fe(OH)₂ and Fe(CO₃)₂²⁻ species contribute over 20% to the rates. Model results show that when the concentration of O₂ is two orders of magnitude higher than the concentration of H₂O₂, the oxidation with O₂ also needs to be considered. The rate constants for the five most kinetically active species (Fe²⁺, FeOH⁺, Fe(OH)₂, FeCO₃, Fe(CO₃)₂²⁻) in seawater as a function of temperature have been determined. The kinetic model is also valid in pure water with different concentrations of HCO₃⁻ and the conditions found in fresh waters.     

An algorithm for finding composition,molar volume and isochors of CO2-CH4 fluid inclusions from Th and Tfm (for Th < Tfm)

A modified Redlich-Kwong equation of state is used to calculate the solubility of CO₂ in methane at various temperatures and pressures. From the solubility of CO₂ in CH₄ at the triple point and at final melting (T_h < T_fm), and the molar volume of solid CO₂, the volume of solid at the triple point, and the molar volume of the inclusion can be calculated using a mass balance. The pressure at the melting point is calculated from the equation of state.The algorithm predicts composition, molar volume, pressure at final melting and the isochor pressure (for a given temperature of trapping) for CO₂-CH₄ fluid inclusions for the case T_h < T_fm, given T_h, T_fm and experimental data on P_h and d_co2 (solid) at T_h.     

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

The rise of trees and their effects on Paleozoic atmospheric CO2 and O2

The rise of large vascular plants during the mid-Paleozoic brought about a major increase in the rates of weathering of silicate minerals that induced a drop in the level of atmospheric CO₂ and contributed, via the atmospheric greenhouse effect, to global cooling and the initiation of the most long lived and a really extensive glaciation of the past 550 million years. Sedimentary burial of the microbiologically resistant remains of the plants resulted during the Permo-Carboniferous in both further lowering of CO₂ and in elevation of atmospheric O₂. Evidence of changes in CO₂ and O₂ are provided by mathematical models, studies of paleosols, fossil plants, fossil insects, and the effects of modern plants on silicate weathering, and by laboratory studies of the effects of changes in O₂ on plants and insects. To cite this article: R.A. Berner, C. R. Geoscience 335 (2003).     

Die Kristallstruktur des Voltaits,K2Fe 5 2+ Fe 3 3+ Al[SO4]12·18H2O

Zusammenfassung Die Kristallstruktur von künstlichem Voltait, K₂Fe₅ ²⁺Fe₃ ³⁺Al[SO₄]₁₂· ·18 H₂O, kubisch hexakisoktaedrisch,Fd3c–O _h ⁸,a ₀=27,254 ,Z-16, wurde mittels photographischer Röntgendaten bestimmt. Die Aufklärung der Struktur erfolgte mit Patterson- und Fouriermethoden unter Zuhilfenahme des multiplen isomorphen Ersatzes. Die Verfeinerung nach der Methode der kleinsten Quadrate ergab mit anisotropen Temperaturfaktoren für 726 beobachteteF _hkl R=0,033. Das Hauptmerkmal der Struktur ist ein 3dimensionales Gerüst aus [Fe³⁺O₆]-Oktaedern, [Fe ₅ ^6/2+ Fe ₁ ^6/3+ O₄(H₂O)₂]-Oktaedern und [K⁺O₁₂]-Polyedern, die durch SO₄-Tetraeder verknüpft werden. Hohlräume dieses Gerüstes werden von ungeordnet orientierten [Al(H₂O)₆]-Oktaedern eingenommen. Es wird gezeigt, daß Al als wesentlicher Bestandteil dieses Voltaits angesehen werden muß.

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The crystal structure of voltaite, K₂Fe₅ ²⁺Fe₃ ³⁺Al[SO₄]₁₂·18H₂O

Summary The crystal structure of synthetic voltaite, K₂Fe₅ ²⁺Fe₃ ³⁺Al[SO₄]₁₂· · 18 H₂O, cubic hexakis-octahedral, space groupFd3c–O _h ⁸,a ₀=27.254 ,Z=16, was determined from photographic X-ray data. The structure was solved by Patterson and Fourier-methods with the aid of multiple isomorphic substitution. Least squares refinement with anisotropic temperature factors resulted inR=0.033 for 726 observedF _hkl . The dominant structural feature is a continous framework composed of [Fe³⁺O₆]-octahedra, [Fe ₅ ^6/2+ Fe ₁ ^6/3+ O₄(H₂O)₂]-octahedra and [K⁺O₁₂]-polyhedra linked by SO₄-tetrahedra. The arrangement gives rise to cages occupied by disordered [Al(H₂O)₆]-octahedra. It is shown that Al must be considered to be a essential constituent of such voltaites.

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Mit 2 Abbildungen     

Tracing high-pressure metamorphism in marbles: Phase relations in high-grade aluminous calcite–dolomite marbles from the Greek Rhodope massif in the system CaO–MgO–Al2O3–SiO2–CO2 and indications of prior aragonite

Four different types of parageneses of the minerals calcite, dolomite, diopside, forsterite, spinel, amphibole (pargasite), (Ti–)clinohumite and phlogopite were observed in calcite–dolomite marbles collected in the Kimi-Complex of the Rhodope Metamorphic Province (RMP). The presence of former aragonite can be inferred from carbonate inclusions, which, in combination with an analysis of phase relations in the simplified system CaO–MgO–Al₂O₃–SiO₂–CO₂ (CMAS–CO₂) show that the mineral assemblages preserved in these marbles most likely equilibrated at the aragonite–calcite transition, slightly below the coesite stability field, at ca. 720 °C, 25 kbar and a_CO2 ~ 0.01. The thermodynamic model predicts that no matter what activity of CO₂, garnet has to be present in aluminous calcite–dolomite-marble at UHP conditions.