Unusual C35 and C36 alkenones in a paleoceanographic benchmark strain of Emiliania huxleyi

Our specimen of the cultured Emiliania huxleyi strain (CCMP1742, also known as NEPCC55a) that provides the benchmark for -based paleothermometry has started producing, for reasons yet unclear, major amounts of three new alkenones identified as ω15,22-C₃₅ methyl ketone, ω15,22-C₃₆ ethyl ketone and ω16,23-C₃₆ methyl ketone. Comparison of these structures with those established now by the same OsO₄ derivatization method applied to the di-unsaturated C₃₇, C₃₈ and C₃₉ alkenones typically found in this organism provides insight into the possible pathway for their biosynthesis. Isothermal batch culture experiments also show the content and composition of these new compounds change systematically and quite significantly in cells when subjected to environmental conditions such as nutrient depletion, variation in light availability and prolonged darkness. Alkenones of similarly unusual short-chain length are evident in suspended particulate materials from present day surface waters in the Ligurian Sea (Mediterranean) and in two different Holocene time horizons (Unit I and Unit II deposits) in Black Sea sediments. However, the positions of the double bonds are different from those that we now report in our culture, implying a different biosynthetic sequence. These alkenones are most likely derived from another, as yet unknown, haptophyte species. If this other organism accounts for all documented occurrences of these compounds in natural samples, then either it has a capacity for growth over a remarkably wide salinity range or surface water salinity in the early Holocene Black Sea may not have been as low as is currently believed.     

Carbon isotopic fractionation during the CO2 exchange process between air and sea water under equilibrium and kinetic conditions

Carbon isotopic fractionation during the air/sea exchange process is not fully understood at present. Information on the equilibrium and kinetic fractionation factors is an essential requirement, together with the value of the CO₂ partial pressure, for understanding the carbon cycle in the atmosphere and marine environments. Using a specially designed countercurrent equilibrator system, the fractionation factors between gaseous CO₂ and dissolved inorganic carbon in sea water were determined under both kinetic and equilibrium conditions. The following results were obtained: kinetic fractionation factor for air to sea (α_as) is 0.998 at 288.2 K; kinetic fractionation factor for sea to air (α_sa) is 0.990; equilibrium fractionation factor (α_eq) is 0.991 at pH = 8.3 and 288.2 K. From these results, the carbon isotopic ratio of CO₂ passed through the air/ sea interface is estimated to be about ?10 %. for air to sea and ?8 %. for sea to air when CO₂ exchange takes place between air (δ¹³C = ?8 %.) and surface sea water (δ¹³C = 2 %.) at 288.2 K.     

Kinetic isotopic fractionation during carbonate dissolution in laboratory experiments: Implications for detection of microbial CO2 signatures using δC-DIC

Laboratory experiments on reagent-grade calcium carbonate and carbonate rich glacial sediments demonstrate previously unreported kinetic fractionation of carbon isotopes during the initial hydrolysis and early stages of carbonate dissolution driven by atmospheric CO₂. There is preferential dissolution of Ca¹²CO₃ during hydrolysis, resulting in δ¹³C-DIC values that are significantly lighter isotopically than the bulk carbonate. The fractionation factor for this kinetic isotopic effect is defined as ε_carb. ε_carb is greater on average for glacial sediments (−17.4‰) than for calcium carbonate (−7.8‰) for the < 63 μm size fraction, a sediment concentration of 5 g L⁻¹ and closed system conditions at 5°C. This difference is most likely due to the preferential dissolution of highly reactive ultra-fine particles with damaged surfaces that are common in subglacial sediments. The kinetic isotopic fractionation has a greater impact on δ¹³C-DIC at higher CaCO₃:water ratios and is significant during at least the first 6 h of carbonate dissolution driven by atmospheric CO₂ at sediment concentrations of 5 g L⁻¹. Atmospheric CO₂ dissolving into solution following carbonate hydrolysis does not exhibit any significant equilibrium isotopic fractionation for at least ∼ 6 h after the start of the experiment at 5°C. This is considerably longer than previously reported in the literature. Thus, kinetic fractionation processes will likely dominate the δ¹³C-DIC signal in natural environments where rock:water contact times are short <6-24 h (e.g., glacial systems, headwaters in fluvial catchments) and there is an excess of carbonate in the sediments. It will be difficult apply conventional isotope mass balance techniques in these types of environment to identify microbial CO₂ signatures in DIC from δ¹³C-DIC data.     

Hydrogen isotopic fractionation in lipid biosynthesis by H2-consuming Desulfobacterium autotrophicum

We report hydrogen isotopic fractionations between water and fatty acids of the sulfate-reducing bacterium Desulfobacterium autotrophicum. Pure cultures were grown in waters with deuterium (D) contents that were systematically varied near the level of natural abundance (−37‰ ? δD ? 993‰). H₂ of constant hydrogen isotope (D/H) ratio was supplied to the cultures. The D/H ratios of water, H₂, and specific fatty acids were measured by isotope-ratio mass spectrometry. The results demonstrate that D. autotrophicum catalyzes hydrogen isotopic exchange between water and H₂, and this reaction is conclusively shown to approach isotopic equilibrium. In addition, variation in the D/H ratio of growth water accounts for all variation in the hydrogen isotopic composition of fatty acids. The D/H ratios of fatty acids from cultures grown on H₂/CO₂ are compared with those from a separate set of cultures grown on D-enriched formate, an alternative electron donor. This comparison rules out H₂ as a significant source of fatty acid hydrogen. Grown on either H₂/CO₂ or formate, D. autotrophicum produces fatty acids in which all hydrogen originates from water. For specific fatty acids, biosynthetic fractionation factors are mostly in the range 0.60 ? α_FA-water ? 0.70; the 18:0 fatty acid exhibits a lower fractionation factor of 0.52. The data show that α_FA-water generally increases with length of the carbon chain from C₁₄ to C₁₇ among both saturated and unsaturated fatty acids. These results indicate a net fractionation associated with fatty acid biosynthesis in D. autotrophicum that is slightly smaller than in another H₂-consuming bacterium (Sporomusa sp.), but much greater than in most photoautotrophs.     

Mitigation of asphaltics deposition during CO2 flood by enhancing CO2 solvency with chemical modifiers

CO₂ injected in the reservoir of McElroy Field, TX, for a CO₂ flood was in the supercritical state. Supercritical CO₂ fluid is capable of extracting light and intermediate hydrocarbons from rocks but is unable to extract heavy hydrocarbons and asphaltics. Therefore, plugging of asphaltics in reservoir rocks and a consequent reduction in injectivity and recovery may result when CO₂ only is used in enhanced oil recovery. By adding common solvents as chemical modifiers, the flooding fluid shows marked improvement in solvency for heavy components of crudes due to its increased density and polarity. Numerous supercritical CO₂ fluid extractions of dolomite rock from the Grayburg Formation containing known amount of spiked McElroy crude oil have been carried out to evaluate extraction efficiencies of CO₂ and CO₂ with chemical modifiers at various temperatures and pressures. All experiments show that extraction efficiency increases with increasing CO₂ pressure but decreases with increasing temperature. Addition of chemical modifiers to CO₂ also shows improved extraction efficiency and reduced asphaltic deposits. Under the pressure and temperature similar to McElroy reservoir conditions; chemically modified CO₂ yielded almost 3 times as much oil extracts as those in extractions with CO₂ only. It also reduced the asphaltics content in extracted rocks to nearly one half; indicating its potential for mitigating asphaltics plugging of formation rocks     

Microbial respiration and diffusive transport of O2, O2, and OO in unsaturated soils: a mesocosm experiment

Although the flux of molecular O₂ between the atmosphere and the subsurface is intrinsically linked to the net soil production of greenhouse gasses, few studies have focused on the controls affecting the isotopic composition of O₂ in the subsurface. Here, we developed and tested a stable oxygen isotope tracer technique and gas transport modeling approach to evaluate O₂ cycling and fluxes from the subsurface that used an environmentally controlled soil mescosm. We measured the O₂ and δ¹⁸O₂ profiles in a model unsaturated soil zone and quantified the O₂ consumption rates and the O₂ isotope fractionation factors resulting from the combined processes of subsurface microbial (including bacteria, fungi, and protozoa) consumption of O₂ and diffusive influx of O₂ from the atmosphere. We found that at high respiration rates in the mesocosm, there appeared to be very little isotope fractionation of O₂ by soil microorganisms. Although the mesocosm respiration rates are not typical of natural soils in northern temperate climes, they may be more representative of soils in warm and moist tropical environments. Our findings caution against the indiscriminate application of laboratory-determined oxygen isotope fractionation factors to field settings. The oxygen isotope tracer and modeling approach demonstrated here may be applied to gain a better understanding of biogenic gas production and O₂ cycling in subsurface systems and soils.     

Characteristics of alkenones synthesized by a bloom of emiliania huxleyi in the Bering Sea

We investigated the characteristics of the alkenones produced by a bloom of Emiliania huxleyi in the eastern Bering Sea in 2000. Alkenones were detected in surface waters between 57°N and 63°N, where phosphate concentrations were low and the ammonium/nitrate ratio was high. The total alkenone content (C_37:2, C_37:3, and C_37:4) ranged from 22.0 to 349 μg g⁻¹ in suspended particles and from 0.109 to 1.42 μg g⁻¹ in surface sediments. This suggests that a large proportion of the particulate alkenones synthesized in the surface water rapidly degraded within the water column and/or at the water-sediment interface of the Bering Shelf. The change in the stable carbon isotopic composition (δ¹³C) of C_37:3 alkenone could not be explained only by variation in [CO₂(aq)] in the surface water but also depended on the growth rate of E. huxleyi. The alkenone unsaturation index (U^K′₃₇) was converted into an alkenone “temperature” with three equations [Prahl et al 1988], [Sikes et al 1997] and [Müller et al 1998]; Sikes et al.’s (1997) equation gave the best correlation with the observed sea surface temperature (SST) in the eastern Bering Sea. However, some temperatures estimated by Sikes et al.’s (1997) equation from the U^K′₃₇ varied from the observed SST, possibly because of the rapidly changing rate of alkenone synthesis in the logarithmic growth stage or the low rate of alkenone synthesis when nutrients were limiting. Temperatures estimated from U^K′₃₇ in the surface sediments (6.8-8.2°C) matched the observed SST in September (7-8°C) but differed from the annual average SST of 4 to 5°C, suggesting that most of the alkenone in the eastern Bering Sea was synthesized during limited periods, for instance, in September. The relative amounts of C_37:4 alkenone as proportions of the total alkenones (referred to as C_37:4%) were high, ranging from 18.3 to 41.4%. Low-salinity water (<32 psu) within the study area would have contributed to the high C_37:4% because a negative linear relationship between C_37:4% and salinity was found in this study.     

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.     

A comparison of isotope fractionation of carbon and hydrogen from paddy field rice roots and soil bacterial enrichments during CO2/H2 methanogenesis

To better understand the isotope biogeochemistry of paddy field CH₄, we investigated carbon and hydrogen isotope fractionation during CO₂ reduction by a methanogenic community enriched from California paddy field soil and rice plants. Results from analyses of terminal restriction fragment length polymorphism (T-RFLP) and sequences of the archaeal small-subunit (SSU) rRNA-encoding genes (rDNA) showed a difference in methanogenic community structure between the soil (dominated by Methanobacteriaceae) and roots (dominated by Methanospirillaceae) which was essentially the same for sampling dates 15 and 99 days after flooding (DAF). CO₂/H₂ methanogenesis by these microbial communities produced CH₄ with different isotope ratios and fractionation factors (α factors). The carbon isotope α factors in an open system with a continuous supply of 0.5% H₂ were 1.050 ± 0.002 and 1.057 ± 0.001 for soil and root enrichment cultures at 15 DAF, and 1.052 ± 0.0.002 and 1.059 ± 0.002 for soil and root enrichment cultures at 99 DAF, respectively. These α factors are similar to, but distinct from values previously obtained from cultures of mesophilic methanogens and are larger than calculated values (1.045) for paddy soil. Fractionation of hydrogen isotopes was also studied in a closed system under 80% H₂. The difference in α factors between soil and root enrichment cultures remained clear. The hydrogen isotope fractionations between culture water and the product CH₄ were −327 ± 14‰ and −319 ± 18‰ for soil enrichments, and −389 ± 17‰ and −382 ± 21‰ for root enrichments at 15 DAF and 99 DAF, respectively.     

Laboratory study of self-potential signals during releasing of CO2 and N2 plumes

Carbon Capture Sequestration (CCS) projects require, for safety reasons, monitoring programmes focused on surveying gas leakage on the surface. Generally, these programmes include detection of chemical tracers that, once on the surface, could be associated with CO₂ degassing. We take a different approach by analysing feasibility of applying electrical surface techniques, specifically Self-Potential. A laboratory-scale model, using water-sand, was built for simulating a leakage scenario being monitored with non-polarisable electrodes. Electrical potentials were measured before, during and after gas injection (CO₂ and N₂) to determine if gas leakage is detectable. Variations of settings were done for assessing how the electrical potentials changed according to size of electrodes, distance from electrodes to the gas source, and type of gas. Results indicated that a degassing event is indeed detectable on electrodes located above injection source. Although the amount of gas could not be quantified from signals, injection timespan and increasing of injection rate were identified. Even though conditions of experiments were highly controlled contrasting to those usually found at field scale, we project that Self-Potential is a promising tool for detecting CO₂ leakage if electrodes are properly placed.     

Behavior of molybdenum in alkali silicate melts: Effects of excess SiO2 and CO2

The effects of excess SiO₂ and CO₂ on the solubility of molybdenite in hydrous sodium disilicate melts were experimentally determined at 680 bars and 650°C. The molybdenite solubility decreases with increasing SiO₂ and CO₂. Under the experimental conditions, the MoS₂ content of the vapor-saturated liquid decreases from 10 wt.% to 2.5 wt.% at SiO₂ saturation. In the presence of CO₂, the solubility decreases to 4.6 wt.% MoS₂ and becomes negligible at high P_CO2. These results are explained as deriving from the increased polymerization and hence decreased NBO/Si ratio of the melt with increasing SiO₂ content and CO₂, respectively. Sulfur dissolves principally as SO₄^?2 at the relatively high fo₂ of the experiments. Consequently, the effect of sulfur is to lower the Mo solubility by effectively decreasing the NBO/Si ratio of the melt. Sulfur saturation is, therefore, likely to be a limiting factor in the Mo content of alkali silicate melts because of the chalcophile affinities of molybdenum.     

Selection of coals of different maturities for CO2 Storage by modelling of CH4 and CO2 adsorption isotherms

CO₂ injection in unmineable coal seams could be one interesting option for both storage and methane recovery processes. The objective of this study is to compare and model pure gas sorption isotherms (CO₂ and CH₄) for well-characterised coals of different maturities to determine the most suitable coal for CO₂ storage. Carbon dioxide and methane adsorption on several coals have been investigated using a gravimetric adsorption method. The experiments were carried out using both CO₂ and CH₄ pure gases at 25 °C from 0.1 to 5 MPa (1 to 50 bar). The experimental results were fitted using Temkin's approach but also with the corrected Langmuir's and the corrected Tóth's equations. The two last approaches are more accurate from a thermodynamical point of view, and have the advantage of taking into account the fact that experimental data (isotherms) correspond to excess adsorption capacities. These approaches allow better quantification of the adsorbed gas. Determined CO₂ adsorption capacities are from 0.5 to 2 mmol/g of dry coal. Modelling provides also the affinity parameters of the two gases for the different coals. We have shown these parameters determined with adsorption models could be used for classification and first selection of coals for CO₂ storage. The affinity ratio ranges from a value close to 1 for immature coals to 41 for high rank coals like anthracites. This ratio allows selecting coals having high CO₂ adsorption capacities. In our case, the modelling study of a significant number of coals from various ranks shows that anthracites seem to have the highest CO₂ storage capacities. Our study provides high quality affinity parameters and values of CO₂ and CH₄ adsorption capacities on various coals for the future modelling of CO₂ injection in coal seams.     

火山岩吸附CO2气的成藏潜力及实例分析

火山岩的脱气实验和对昌德东CO2气藏气源的分析结果表明加热火山岩到250℃时,脱出挥发分总量为0.0299～0.0790mL/g,其中CO2脱出量为0.0218～0.0706mL/g(0.429～1.387wt%);挥发组分以CO2为主,还含有H2、CO、CH4等还原性气体,以及少量低碳烷烃,CO2含量和总烃呈现反比关系;基性岩的CO2脱出量、脱出率高于中、酸性岩;CO2脱出量与岩石碱质含量正相关.松辽盆地北部昌德东CO2气藏成藏模式为"自生自储",成藏CO2气主要来自深部被火山岩吸附的气.随岩浆上升,在岩浆冷凝成火山岩的过程中被吸附于火山岩的节理、劈理和晶体位错之中的CO2气,连同火山岩包体中的残留气,成为高纯CO2气藏的主要补给源,并非地幔气体沿大断裂上来直接充注成藏.     

Carbon isotopic fractionation by the marine diatom Phaeodactylum tricornutum under nutrient- and light-limited growth conditions

A theoretical model was developed to explain the characteristics of carbon isotopic fractionation (ε_P) by the marine diatom Phaeodactylum tricornutum under nutrient- and light-limited growth conditions. The model takes into consideration active transport and diffusion of inorganic carbon through the cell membrane and chloroplast membrane and the energetic tradeoff between production of Rubisco and operation of a carbon-concentrating mechanism to achieve a given growth rate. The model is able to explain 88% of the variance in experimental ε_p data reported in this study and in previous work and is able to account for the observed pattern of Rubisco activity in nitrate-limited chemostats. Two important implications of the model include the fact that ε_p is not a unique function of the ratio of growth rate to external CO₂ concentration (as opposed to the predictions of several previous models) and that changes in light-limited and nutrient-limited growth rates have opposite effects on the fraction of CO₂ taken up by the chloroplast that is lost to diffusion and hence on certain patterns of carbon isotopic fractionation.     

Temperature dependence of oxygen isotope fractionation of CO2 from magnesite-phosphoric acid reaction

New experimental results are reported on oxygen isotope fractionation factors, α_T, between the δ¹⁸O compositions of carbon dioxide liberated by phosphoric acid in the temperature interval of 323 to 373K and that of total oxygen from a natural magnesite (MgCO₃). These results are distinctly different from some previously published mutually inconsistent data, and can be expressed as a linear relationship: 10³ lnα_T = [{(6.845 ± 0.475)∗10⁵}/T²] + (4.22 ± 0.08), where 10³ lnα_T refers to fractionation at different temperatures T in Kelvin.Fractionation factors have also been determined at 323 and 368K on a natural calcite. The results on calcite are in excellent agreement with previously published data and can be written as:10³ lnα_T = [{(5.608 ± 0.151)∗10⁵}/T²] + (3.89 ± 0.08).The combined results on magnesite and calcite yield a computed value of α = 1.01117 for dolomite at 298K, assuming equal proportion of 0.5 mole of magnesium and calcium in dolomite, the previously reported experimental values being 1.01109 and 1.01110.     

Correction of ground-water chemistry and carbon isotopic composition for effects of CO2 outgassing

Direct measurements on water samples from several CO₂-charged warm springs are significantly higher than values calculated from field pH and alkalinity (and other constituents). In addition, calcite saturation indices calculated from field pH and solution composition indicated supersaturation in samples which, on the basis of hydrogeologic concepts, should be near saturation or undersaturated. We attribute these discrepancies to uncertainties in field pH, resulting from CO₂ outgassing during pH measurement. Because samples for direct measurement can be taken with minimal disturbance to the water chemistry, we have used the measured to back calculate an estimate of the field pH and the carbon isotopic composition of the water before outgassing. By reconstructing water chemistry in this way, we find generally consistent grouping of $\text{δ}{}^{13}\text{C}$, pH, and degree of calcite saturation in samples taken from the same source at different times, an observation which we expect based on our understanding of the hydrogeology and geochemistry of the ground-water systems. This suggests that for very careful geochemical work, particularly on ground-waters much above ambient temperature, measurements may provide more information on the system and a better estimate of its state of saturation with respect to carbonate minerals than can field measurements of pH.     

BRYOCARB: A process-based model of thallose liverwort carbon isotope fractionation in response to CO2, O2, light and temperature

Evidence from laboratory experiments indicates that fractionation against the heavy stable isotope of carbon (Δ¹³C) by bryophytes (liverworts and mosses) is strongly dependent on atmospheric CO₂. This physiological response may therefore provide the basis for developing a new terrestrial CO₂ proxy [Fletcher, B.J., Beerling, D.J., Brentnall, S.J., Royer, D.L., 2005. Fossil bryophytes as recorders of ancient CO₂ levels: experimental evidence and a Cretaceous case study. Global Biogeochem. Cycles19, GB3012]. Here, we establish a theoretical basis for the proxy by developing an extended model of bryophyte carbon isotope fractionation (BRYOCARB) that integrates the biochemical theory of photosynthetic CO₂ assimilation with controls on CO₂ supply by diffusion from the atmosphere. The BRYOCARB model is evaluated against measurements of the response of liverwort photosynthesis and Δ¹³C to variations in atmospheric O₂, temperature and irradiance at different CO₂ concentrations. We show that the bryophyte proxy is at least as sensitive to variations in atmosphere CO₂ as the two other leading carbon isotope-based approaches to estimating palaeo-CO₂ levels (δ¹³C of phytoplankton and of paleosols). Mathematical inversion of BRYOCARB provides a mechanistic means of estimating atmospheric CO₂ levels from fossil bryophyte carbon that can explicitly account for the effects of past differences in O₂ and climate.     

Caprock interaction with CO2: A laboratory study of reactivity of shale with supercritical CO2 and brine

Crushed rock from two caprock samples, a carbonate-rich shale and a clay-rich shale, were reacted with a mixture of brine and supercritical CO₂ (CO₂–brine) in a laboratory batch reactor, at different temperature and pressure conditions. The samples were cored from a proposed underground CO₂ storage site near the town of Longyearbyen in Svalbard. The reacting fluid was a mixture of 1 M NaCl solution and CO₂ (110 bar) and the water/rock ratio was 20:1. Carbon dioxide was injected into the reactors after the solution had been bubbled with N₂, in order to mimic O₂-depleted natural storage conditions. A control reaction was also run on the clay-rich shale sample, where the crushed rock was reacted with brine (CO₂-free brine) at the same experimental conditions. A total of 8 batch reaction experiments were run at temperatures ranging from 80 to 250 °C and total pressures of 110 bar (∼40 bar for the control experiment). The experiments lasted 1–5 weeks.Fluid analysis showed that the aqueous concentration of major elements (i.e. Ca, Mg, Fe, K, Al) and SiO₂ increased in all experiments. Release rates of Fe and SiO₂ were more pronounced in solutions reacted with CO₂–brine as compared to those reacted with CO₂-free brine. For samples reacted with the CO₂–brine, lower temperature reactions (80 °C) released much more Fe and SiO₂ than higher temperature reactions (150–250 °C). Analysis by SEM and XRD of reacted solids also revealed changes in mineralogical compositions. The carbonate-rich shale was more reactive at 250 °C, as revealed by the dissolution of plagioclase and clay minerals (illite and chlorite), dissolution and re-precipitation of carbonates, and the formation of smectite. Carbon dioxide was also permanently sequestered as calcite in the same sample. The clay-rich shale reacted with CO₂–brine did not show major mineralogical alteration. However, a significant amount of analcime was formed in the clay-rich shale reacted with CO₂-free brine; while no trace of analcime was observed in either of the samples reacted with CO₂–brine.     

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.     

CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids: Implications for modeling the solubility of CO2 in silicic melts

The solubility of CO₂ in dacitic melts equilibrated with H₂O-CO₂ fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO₂ is dissolved in dacitic glasses as molecular CO₂ and carbonate. The quantification of total CO₂ in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm⁻¹ can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO_2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO₂ species concentrations from the MIR spectra we have measured total CO₂ contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO₂ solubility in dacitic melts on x^fluid_CO2,total shows a strong positive deviation from linearity with almost constant CO₂ solubility at x_CO2fluid > 0.8 (maximum CO₂ solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO₂. A similar nonlinear variation of CO₂ solubility with x_CO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO₂ (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO₂ molecules.A thermodynamic model describing the dependence of the CO₂ solubility in hydrous rhyolitic and dacitic melts on T, P, f_CO2 and the mol fraction of water in the melt (x_water) has been developed. An exponential variation of the equilibrium constant K₁ with x_water is proposed to account for the nonlinear dependence of x_CO2,totalmelt on x_CO2fluid. The model reproduces the CO₂ solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low x_CO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO₂ at low pressures (a Henrian behavior of the CO₂ solubility is observed at low pressure and low H₂O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the x_CO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO₂ is much lower in rhyolitic melts (31.7 cm³/mol) than in dacitic melts (46.6 cm³/mol). The dissolution enthalpy for CO₂ in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO₂ solubility in silicic melts.