CO2-induced dissolution of low permeability carbonates. Part II: Numerical modeling of experiments

We used the 3D continuum-scale reactive transport models to simulate eight core flood experiments for two different carbonate rocks. In these experiments the core samples were reacted with brines equilibrated with pCO₂ = 3, 2, 1, 0.5 MPa (Smith et al., 2013 [27]). The carbonate rocks were from specific Marly dolostone and Vuggy limestone flow units at the IEAGHG Weyburn-Midale CO₂ Monitoring and Storage Project in south-eastern Saskatchewan, Canada. Initial model porosity, permeability, mineral, and surface area distributions were constructed from micro tomography and microscopy characterization data. We constrained model reaction kinetics and porosity–permeability equations with the experimental data. The experimental data included time-dependent solution chemistry and differential pressure measured across the core, and the initial and final pore space and mineral distribution. Calibration of the model with the experimental data allowed investigation of effects of carbonate reactivity, flow velocity, effective permeability, and time on the development and consequences of stable and unstable dissolution fronts.The continuum scale model captured the evolution of distinct dissolution fronts that developed as a consequence of carbonate mineral dissolution and pore scale transport properties. The results show that initial heterogeneity and porosity contrast control the development of the dissolution fronts in these highly reactive systems. This finding is consistent with linear stability analysis and the known positive feedback between mineral dissolution and fluid flow in carbonate formations. Differences in the carbonate kinetic drivers resulting from the range of pCO₂ used in the experiments and the different proportions of more reactive calcite and less reactive dolomite contributed to the development of new pore space, but not to the type of dissolution fronts observed for the two different rock types. The development of the dissolution front was much more dependent on the physical heterogeneity of the carbonate rock. The observed stable dissolution fronts with small but visible dissolution fingers were a consequence of the clustering of a small percentage of larger pores in an otherwise homogeneous Marly dolostone. The observed wormholes in the heterogeneous Vuggy limestone initiated and developed in areas of greater porosity and permeability contrast, following pre-existing preferential flow paths.Model calibration of core flood experiments is one way to specifically constrain parameter input used for specific sites for larger scale simulations. Calibration of the governing rate equations and constants for Vuggy limestones showed that dissolution rate constants reasonably agree with published values. However the calcite dissolution rate constants fitted to the Marly dolostone experiments are much lower than those suggested by literature. The differences in fitted calcite rate constants between the two rock types reflect uncertainty associated with measured reactive surface area and appropriately scaling heterogeneous distribution of less abundant reactive minerals. Calibration of the power-law based porosity–permeability equations was sensitive to the overall heterogeneity of the cores. Stable dissolution fronts of the more homogeneous Marly dolostone could be fit with the exponent n = 3 consistent with the traditional Kozeny–Carman equation developed for porous sandstones. More impermeable and heterogeneous cores required larger n values (n = 6–8).     

Co-sequestration of SO2 with supercritical CO2 in carbonates: An experimental study of capillary trapping,relative permeability,and capillary pressure

In this study we performed three categories of steady- and unsteady-state core-flooding experiments to investigate capillary trapping, relative permeability, and capillary pressure, in a scCO₂ + SO₂/brine/limestone system at elevated temperature and pressure conditions, i.e., 60 °C and 19.16 MPa. We used a Madison limestone core sample acquired from the Rock Springs Uplift in southwest Wyoming. We carried out two sets of steady-state drainage-imbibition relative permeability experiments with different initial brine saturations to study hysteresis. We found that the final scCO₂ + SO₂ drainage relative permeability was very low, i.e., 0.04. We also observed a rapid reduction in the scCO₂-rich phase imbibition relative permeability curve, which resulted in a high residual trapping. The results showed that between 62.8% and more than 76% of the initial scCO₂ + SO₂ at the end of drainage was trapped by capillary trapping mechanism (trapping efficiency). We found that at higher initial brine saturations, the trapping efficiency was higher. The maximum initial and residual scCO₂-rich phase saturations at the end of primary drainage and imbibition were 0.525 and 0.329, respectively. Each drainage-imbibition cycle was followed by a dissolution process to re-establish S_w = 1. The dissolution brine relative permeabilities for both cycles were also obtained. We characterized the scCO₂ + SO₂/brine capillary pressure hysteresis behavior through unsteady-state primary drainage, imbibition, and secondary drainage experiments. We observed negative imbibition capillary pressure curve indicative of possible wettability alteration throughout the experiments due to contact with scCO₂ + SO₂/brine fluid system. The trapping results were compared to those reported in literature for other carbonate core samples. We noticed slightly more residual trapping in our sample, which might be attributed to heterogeneity, different viscosity ratio, and pore-space topologies. The impact of dynamic effects, i.e., high brine flow rate imbibition tests, on trapping of the scCO₂-rich phase was also explored. We performed two imbibition experiments with relatively high brine flow rates. The residual scCO₂ saturation dropped to 0.291 and 0.262 at the end of the first and second imbibition tests, i.e., 11.5% and 20.4%, respectively, compared to 0.329 under capillary-dominated regime.     

Pore-scale contact angle measurements at reservoir conditions using X-ray microtomography

Contact angle is a principal control of the flow of multiple fluid phases through porous media; however its measurement on other than flat surfaces remains a challenge. A new method is presented for the measurement of the contact angle between immiscible fluids at the pore scale at reservoir conditions (10 MPa and 50 °C) inside a quarry limestone through the use of X-ray microtomography. It is applied to a super-critical CO₂–brine–carbonate system by resampling the micro-CT data onto planes orthogonal to the contact lines, allowing for vectors to be traced along the grain surface and the CO₂–brine interface. A distribution of contact angles ranging from 35° to 55° is observed, indicating that the CO₂–brine–carbonate system is weakly water-wet. This range of contact angles can be understood as the result of contact angle hysteresis and surface heterogeneity on a range of length scales. Surface heterogeneity is examined by comparison of micro-CT results with optical thin sections and SEM images.     

A new unsteady-state method of determining two-phase relative permeability illustrated by CO2-brine primary drainage in berea sandstone

This study presents a new unsteady-state method for measuring two-phase relative permeability by obtaining local values of the three key parameters (saturation, pressure drop, and phase flux) versus time during a displacement. These three parameters can be substituted to two-phase Darcy Buckingham equation to directly determine relative permeability. To obtain the first two, we use a medical X-ray Computed Tomography (CT) scanner to monitor saturation in time and space, and six differential pressure transducers to measure the overall pressure drop and the pressure drops of five individual sections (divided by four pressure taps on the core) continuously. At each scanning time, the local phase flux is obtained by spatially integrating the saturation profile and converting this to the flux using a fractional flow framework. One advantage of this local method over most previous methods is that the capillary end effect is experimentally avoided; this improvement is crucial for experiments using low viscosity fluids such as supercritical and gas phases. To illustrate the new method, we conduct five CO₂-brine primary drainage experiments in a 60.8 cm long and 116 mD Berea sandstone core at 20 °C and 1500 psi. In return, we obtain hundreds of unsteady-state CO₂ and brine relative permeability data points that are consistent with steady-state relative permeability data from the same experiments. Due to the large amount of relative permeability data obtained by the new unsteady-state method, the uncertainties of the exponents in the Corey-type fits decrease by up to 90% compared with the steady-state method.     

Cave air ventilation and CO2 outgassing by radon-222 modeling: How fast do caves breathe?

In general, the rate and timing of calcite precipitation is in part affected by variations in cave air CO₂ concentrations. Knowledge of cave ventilation processes is required to quantify the effect variations in CO₂ concentrations have on speleothem deposition rates and thus paleoclimate records. In this study we use radon-222 (²²²Rn) as a proxy of ventilation to estimate CO₂ outgassing from the cave to the atmosphere, which can be used to infer relative speleothem deposition rates. Hollow Ridge Cave, a wild cave preserve in Marianna, Florida, is instrumented inside and out with multiple micro-meteorological sensor stations that record continuous physical and air chemistry time-series data. Our time series datasets indicate diurnal and seasonal variations in cave air ²²²Rn and CO₂ concentrations, punctuated by events that provide clues to ventilation and drip water degassing mechanisms. Average cave air ²²²Rn and CO₂ concentrations vary seasonally between winter (²²²Rn = 50 dpm L^? 1, where 1 dpm L^? 1 = 60 Bq m^? 3; CO₂ = 360 ppmv) and summer (²²²Rn = 1400 dpm L^? 1; CO₂ = 3900 ppmv). Large amplitude diurnal variations are observed during late summer and autumn (²²²Rn = 6 to 581 dpm L^? 1; CO₂ = 360 to 2500 ppmv).We employ a simple first-order ²²²Rn mass balance model to estimate cave air exchange rates with the outside atmosphere. Ventilation occurs via density driven flow and by winds across the entrances which create a ‘venturi’ effect. The most rapid ventilation occurs 25 m inside the cave near the entrance: 45 h^? 1 (1.33 min turnover time). Farther inside (175 m) exchange is slower and maximum ventilation rates are 3 h^? 1 (22 min turnover time). We estimate net CO₂ flux from the epikarst to the cave atmosphere using a CO₂ mass balance model tuned with the ²²²Rn model. Net CO₂ flux from the epikarst is highest in summer (72 mmol m^? 2 day^? 1) and lowest in late autumn and winter (12 mmol m^? 2 day^? 1). Modeled ventilation and net CO₂ fluxes are used to estimate net CO₂ outgassing from the cave to the atmosphere. Average net CO₂ outgassing is positive (net loss from the cave) and is highest in late summer and early autumn (about 4 mol h^? 1) and lowest in winter (about 0.5 mol h^? 1). Modeling of ventilation, net CO₂ flux from the epikarst, and CO₂ outgassing to the atmosphere from cave monitoring time-series can help better constrain paleoclimatic interpretations of speleothem geochemical records.     

A combined glass dissolution/diffusion experiment in Boom Clay at 30 °C

At the appropriate times, silica diffusion in clay is possibly the rate determining process for the dissolution of vitrified waste disposed of in a clay layer. For testing this hypothesis, combined glass dissolution/silica diffusion experiment are performed. SON68 glass coupons doped with the radioactive tracer ³²Si are sandwiched between two cores of humid Boom Clay, heated to 30 °C. Due to glass dissolution, ³²Si is released and diffuses into the clay. At the end of an experiment, the mass loss of the glass coupon is measured and the clay core is sliced to determine the diffusion profile of the ³²Si released from the glass in the clay.Both mass loss and the ³²Si diffusion profile in the clay are described well by a model combining glass dissolution according to a linear rate law with silica diffusion in the clay. Fitting the experiments to this model leads to an apparent silica diffusion coefficient in the clay between 7 × 10⁻¹³ m²/s and 1.2 × 10⁻¹² m²/s. Previously determined values from diffusion experiments at 25 °C are around 6 × 10⁻¹³ m²/s (In-Diffusion experiments) and 2 × 10⁻¹³ m²/s (percolation experiments). The maximal glass dissolution rate for glass next to clay is around 1.6 × 10⁻⁷ g glass/m² s (i.e. 0.014 g glass/m² day). In undisturbed clay, the measured silica concentration is around 5 mg/L. Combining these values with the previously measured (In-Diffusion experiments) product of accessible porosity and retardation factor, leads in two ways to a silica glass saturation concentration in clay between 8 and 10 mg Si/L.Another candidate for the rate determining process of the dissolution of vitrified waste disposed in a clay layer is silica precipitation. Although silica precipitation due to glass dissolution has been shown experimentally at 90 °C, extending the model with silica precipitation does not lead to much better fits, nor could meaningful values of a possible precipitation rate be obtained.     

Carbon-isotope record of the Early Jurassic (Toarcian) Oceanic Anoxic Event from fossil wood and marine carbonate (Lusitanian Basin,Portugal)

The Toarcian Oceanic Anoxic Event (OAE) in the Early Jurassic (∼ 183 Ma ago) was characterized by widespread near-synchronous deposition of organic-rich shales in marine settings, as well as perturbations to several isotopic systems. Characteristically, two positive carbon-isotope excursions in a range of materials are separated by an abrupt negative shift. Carbon-isotope profiles from Toarcian fossil wood collected in England and Denmark have previously been shown to exhibit this large drop (∼ − 7‰) in δ¹³C values, interpreted as due to an injection of isotopically light CO₂ into the ocean–atmosphere system. However, the global nature of this excursion has been challenged on the basis of carbon-isotope data from nektonic marine molluscs (belemnites), which exhibit heavier than expected carbon-isotope values. Here we present new data, principally from fossil wood and bulk carbonate collected at centimetre scale from a hemipelagic section at Peniche, coastal Portugal. This section is low in organic carbon (average TOC = ∼ 0.5%), and the samples should not have suffered significant diagenetic contamination by organic carbon of marine origin. The carbon-isotope profile based on wood shows two positive excursions separated by a large and abrupt negative excursion, which parallels exactly the profile based on bulk carbonate samples from the same section, albeit with approximately twice the amplitude (∼ − 8‰ in wood versus ∼ − 3.5‰ in carbonate). These data indicate that the negative carbon-isotope excursion affected the atmosphere and, by implication, the global ocean as well. The difference in amplitude between terrestrial organic and marine carbonate curves can be explained by greater water availability in the terrestrial environment during the negative excursion, for which there is independent evidence from marine osmium-isotope records and, plausibly, changes in atmospheric CO₂ content, for which independent evidence is also available. The Peniche succession is also notable for the occurrence of re-deposited sediments: their lowest occurrence coincides with the base of the negative excursion and their highest occurrence coincides with its top. Thus, slope instability and sediment supply could have been strongly linked to the global environmental perturbation, an association that may misleadingly simulate the effects of sea-level fall.     

Deep pooling of low degree melts and volatile fluxes at the 85°E segment of the Gakkel Ridge: Evidence from olivine-hosted melt inclusions and glasses

We present new analyses of volatile, major, and trace elements for a suite of glasses and melt inclusions from the 85°E segment of the ultra-slow spreading Gakkel Ridge. Samples from this segment include limu o pele and glass shards, proposed to result from CO₂-driven explosive activity. The major element and volatile compositions of the melt inclusions are more variable and consistently more primitive than the glass data. CO₂ contents in the melt inclusions extend to higher values (167–1596 ppm) than in the co-existing glasses (187–227 ppm), indicating that the melt inclusions were trapped at greater depths. These melt inclusions record the highest CO₂ melt concentrations observed for a ridge environment. Based on a vapor saturation model, we estimate that the melt inclusions were trapped between seafloor depths (～ 4 km) and ～ 9 km below the seafloor. However, the glasses are all in equilibrium with their eruption depths, which is inconsistent with the rapid magma ascent rates expected for explosive activity. Melting conditions inferred from thermobarometry suggest relatively deep (25–40 km) and cold (1240°–1325 °C) melting conditions, consistent with a thermal structure calculated for the Gakkel Ridge. The water contents and trace element compositions of the melt inclusions and glasses are remarkably homogeneous; this is an unexpected result for ultra-slow spreading ridges, where magma mixing is generally thought to be less efficient based on the assumption that steady-state crustal magma chambers are absent in these environments. All melts can be described by a single liquid line of descent originating from a pooled melt composition that is consistent with the aggregate melt calculated from a geodynamic model for the Gakkel Ridge. These data suggest a model in which deep, low degree melts are efficiently pooled in the upper mantle (9–20 km depth), after which crystallization commences and continues during ascent and eruption. Based on our melting model and the assumption that CO₂ is perfectly incompatible, we show that the highest CO₂ concentrations of the melt inclusions (～ 1600 ppm) are consistent with the calculated CO₂ concentrations of primary undegassed melts. The highest measured CO₂/Nb ratio (443) of Gakkel Ridge melt inclusions predicts a mantle CO₂ content of 134 ppm and would result in a global ridge flux of 2.0 × 10¹² mol CO₂/yr.     

Himalayan metamorphic CO2 fluxes: Quantitative constraints from hydrothermal springs

Hot springs in the Marsyandi Valley, Nepal, vent CO₂ sourced from metamorphic fluids that mix with shallow groundwaters before degassing near the Earth's surface. The δ¹³C of spring waters ranges up to + 13‰, while that of the coexisting free gas phase is close to ? 4‰. Empirical and thermodynamic modelling of this isotopic fractionation suggests > 97 ± 1% CO₂ degassing. The calculated minimum total CO₂ degassing in the Marsyandi catchment is 5.4 × 10⁹ mol/yr from a Cl-based estimate of the spring water discharge to the Marsyandi River and the fraction of CO₂ degassed. Extrapolated to the whole of the Himalayas, this implies a probable minimum metamorphic CO₂ flux of 0.9 × 10¹² mol/yr, or ～ 13% of solid Earth CO₂ degassing. The calculated flux is a factor of three greater than the estimated CO₂ drawdown by silicate weathering in the Himalayas. Himalayan metamorphic degassing contributes a significant fraction of the global solid Earth CO₂ flux and implies that metamorphism may cause changes in long-term climate that oppose those resulting from the orogenic forcing of chemical weatherability.     

UV camera measurements of fumarole field degassing (La Fossa crater,Vulcano Island)

The UV camera is becoming an important new tool in the armory of volcano geochemists to derive high time resolution SO₂ flux measurements. Furthermore, the high camera spatial resolution is particularly useful for exploring multiple-source SO₂ gas emissions, for instance the composite fumarolic systems topping most quiescent volcanoes. Here, we report on the first SO₂ flux measurements from individual fumaroles of the fumarolic field of La Fossa crater (Vulcano Island, Aeolian Island), which we performed using a UV camera in two field campaigns: in November 12, 2009 and February 4, 2010. We derived ~ 0.5 Hz SO₂ flux time-series finding fluxes from individual fumaroles, ranging from 2 to 8.7 t d^?1, with a total emission from the entire system of ~ 20 t d^?1 and ~ 13 t d^?1, in November 2009 and February 2010 respectively. These data were augmented with molar H₂S/SO₂, CO₂/SO₂ and H₂O/SO₂ ratios, measured using a portable MultiGAS analyzer, for the individual fumaroles. Using the SO₂ flux data in tandem with the molar ratios, we calculated the flux of volcanic species from individual fumaroles, and the crater as a whole: CO₂ (684 t d^?1 and 293 t d^?1), H₂S (8 t d^?1 and 7.5 t d^?1) and H₂O (580 t d^?1 and 225 t d^?1).     

Rapid imbibition of water in fractures within unsaturated sedimentary rock

The spontaneous imbibition of water and other liquids into gas-filled fractures in variably-saturated porous media is important in a variety of engineering and geological contexts. However, surprisingly few studies have investigated this phenomenon. We present a theoretical framework for predicting the 1-dimensional movement of water into air-filled fractures within a porous medium based on early-time capillary dynamics and spreading over the rough surfaces of fracture faces. The theory permits estimation of sorptivity values for the matrix and fracture zone, as well as a dispersion parameter which quantifies the extent of spreading of the wetting front. Quantitative data on spontaneous imbibition of water in unsaturated Berea sandstone cores were acquired to evaluate the proposed model. The cores with different permeability classes ranging from 50 to 500 mD and were fractured using the Brazilian method. Spontaneous imbibition in the fractured cores was measured by dynamic neutron radiography at the Neutron Imaging Prototype Facility (beam line CG-1D, HFIR), Oak Ridge National Laboratory. Water uptake into both the matrix and the fracture zone exhibited square-root-of-time behavior. The matrix sorptivities ranged from 2.9 to 4.6 mm s^−0.5, and increased linearly as the permeability class increased. The sorptivities of the fracture zones ranged from 17.9 to 27.1 mm s^−0.5, and increased linearly with increasing fracture aperture width. The dispersion coefficients ranged from 23.7 to 66.7 mm² s⁻¹ and increased linearly with increasing fracture aperture width and damage zone width. Both theory and observations indicate that fractures can significantly increase spontaneous imbibition in unsaturated sedimentary rock by capillary action and surface spreading on rough fracture faces. Fractures also increase the dispersion of the wetting front. Further research is needed to investigate this phenomenon in other natural and engineered porous media.     

Inorganic carbon and nutrient fluxes on the Arctic Shelf

Historic data from the Russian-American Hydrochemical Atlas of Arctic Ocean together with data from the TRANSDRIFT II 1994 and TUNDRA 1994 cruises have been used to assess the spatial and inter-annual variability of carbon and nutrient fluxes, as well as air–sea CO₂ exchange in the Laptev and western East Siberian Seas during the summer season. Budget computations using summer data of dissolved inorganic phosphate (DIP), dissolved inorganic nitrogen (DIN) and dissolved inorganic carbon (DIC) gives that the Laptev Sea shelf is a net sink of DIP and DIN of 2.5×10⁶, 23.2×10⁶ mol d⁻¹, respectively, while it is a net source of DIC (excluding air–sea exchange) of 1249×10⁶ mol d⁻¹. In the East Siberian Seas the budget computations give 0.5×10⁶, −11.4×10⁶ and −173×10⁶ mol d⁻¹ (minus being a sink) for DIP, DIN, and DIC, respectively. In summers, the Laptev Sea Shelf is net autotrophic while the East-Siberian Sea Shelf is net heterotrophic, and both systems are weak net denitrifying. The Laptev Sea Shelf takes up 2.1 mmol CO₂ m⁻² d⁻¹ from atmosphere, whereas the western part of the East-Siberian Sea Shelf loose 0.3 mmol CO₂ m⁻² d⁻¹ to the atmosphere. The variability of DIP, DIN and DIC fluxes during summer in the different regions of the Laptev and East Siberian Seas depends on bottom topography, river runoff, exchange with surrounding seas and wind field.     

The Himalayan foreland basin crust and upper mantle

Modeling of multimode surface wave group velocity dispersion data sampling the eastern and the western Ganga basins, reveals a three layer crust with an average V_s of 3.7 km s^?1, draped by ～2.5 km foreland sediments. The Moho is at a depth of 43 ± 2 km and 41 ± 2 km beneath the eastern and the western Ganga basins respectively. Crustal V_p/V_s shows a felsic upper and middle crust beneath the eastern Ganga basin (1.70) compared to a more mafic western Ganga basin crust (1.77). Due to higher radiogenic heat production in felsic than mafic rocks, a lateral thermal heterogeneity will be present in the foreland basin crust. This heterogeneity had been previously observed in the north Indian Shield immediately south of the foreland basin and must also continue northward below the Himalaya. The high heat producing felsic crust, underthrust below the Himalayas could be an important cause for melting of midcrustal rocks and emplacement of leucogranites. This is a plausible explanation for abundance of leucogranites in the east-central Himalaya compared to the west. The uppermost mantle V_s is also significantly lower beneath the eastern Ganga basin (4.30 km s^?1) compared to the west (4.44 km s^?1).     

Potential application of activated carbon from maize tassel for the removal of heavy metals in water

Water-pollution problems worldwide have led to an acute shortage of clean and pure water for both domestic and human consumption. Various technologies and techniques are available for water treatment which includes the use of activated carbon. In this study activated carbons used for the removal of lead (II) ions from water samples were prepared from maize tassels (an agricultural waste residue) which were modified using physical and chemical activation. In the physical activation CO₂ was used as the activating agent, while in chemical activation H₃PO₄ with an impregnation ratio ranging from 1 to 4 was employed. The maize tassel was pyrolysed at different temperatures ranging from 300 °C to 700 °C in an inert atmosphere for a period of 60 min and activated at 700 °C for 30 min. The effects of activation temperature, impregnation ratio and duration were examined. The resultant modified tassels were characterised by measuring their particle-size distribution, porosities, pore volume, and pore-size distribution using scanning electron microscopy (SEM). The activated carbon produced by chemical activation had the highest BET surface area ranging from 623 m² g⁻¹ to 1 262 m² g⁻¹. The surface chemistry characteristics of the modified tassels were determined by FT–IR spectroscopy and Boehm’s titration method. The experimental data proved that properties of activated carbon depend on final temperature of the process, impregnation ratio and duration of the treatment at final temperature. The adsorption studies showed that chemically prepared activated carbon performed better than physically prepared activated carbon.     

Partial pressure and air–sea CO2 flux in the Aegean Sea during February 2006

Data on the distribution of fCO₂ were obtained during a cruise in the Aegean Sea during February 2006. The fCO₂ of surface water (fCO₂^sw) was lower than the atmospheric fCO₂ (fCO₂^atm) throughout the area surveyed and ΔfCO₂ values varied from ?34 to ?61 μatm. The observed under-saturation suggests that surface waters in the Aegean represent a sink for atmospheric CO₂ during the winter of 2006. Higher fCO₂^sw values were recorded in the ‘less warm’ and ‘less saline’ shallow northernmost part of the Aegean Sea implying that the lower seawater temperature and salinity in this area play a crucial role in the spatial distribution of fCO₂^sw.A first estimate of the magnitude of the air–sea CO₂ exchange and the potential role of the Aegean Sea in the transfer of atmospheric CO₂ was also obtained. The air–sea CO₂ fluxes calculated using different gas transfer formulations showed that during February 2006, the Aegean Sea absorbs atmospheric CO₂ at a rate ranging from ?6.2 to ?11.8 mmol m^?2 d^?1 with the shipboard recorded wind speeds and at almost half rate (?3.5 to ?5.5 mmol m^?2 d^?1) with the monthly mean model-derived wind speed. Compared to recent observations from other temperate continental shelves during winter period, the Aegean Sea acts as a moderate to rather strong sink for atmospheric CO₂.Further investigations, including intensive spatial and temporal high-resolution observations, are necessary to elucidate the role of the Aegean Sea in the process of transfer of atmospheric CO₂ into the deep horizons of the Eastern Mediterranean.     

Os isotope heterogeneity of the upper mantle: Evidence from the Mayarí–Baracoa ophiolite belt in eastern Cuba

In an attempt to quantify the extent of geochemical heterogeneity within a restricted and well dated portion of the upper mantle, 27 chromite separates from the 90 My old chromite deposits in the Mayarí–Baracoa ophiolite belt in eastern Cuba have been investigated for platinum group element (PGE) concentrations and Re–Os isotopic systematics. The samples are characterized by systematically subchondritic initial ¹⁸⁷Os/¹⁸⁸Os ratios and substantial heterogeneity. The initial ¹⁸⁷Os/¹⁸⁸Os ratios vary with chromite chemistry and with geographical distribution, reflecting differences in the Os isotopic evolution for the different upper mantle sections represented by the ophiolite. Accordingly, the Os isotope data might be divided into three groups. In the Moa–Baracoa district, where the chromite bodies are located in the mantle–crust transition zone, the calculated initial γOs values average − 0.97 ± 0.69 (n = 13). In the Sagua de Tanamo district, where chromite chemistry is highly variable and their location in relation the mantle sequence is less clear, the initial γOs values are intermediate, with an average of − 1.77 ± 0.80 (n = 7). In the Mayarí district, where the chromite bodies are located in the lower part of the mantle sequence, initial γOs values average − 2.66 ± 0.29 (n = 7). These subchondritic (i.e. negative) initial γOs values are most simply explained by Re depletion during ancient partial melting and/or melt percolation events.The Os isotope heterogeneity documented here indicates a high degree of geochemical complexity on small to intermediate length scales in the upper mantle. Our results, in combination with data on chromites from the literature, show that an “average present-day Os isotopic composition” for the hypothetical depleted MORB mantle (DMM) reservoir cannot be precisely established beyond the statement that it is “broadly chondritic”. Indeed, the upper mantle cannot be considered a sufficiently homogeneous geochemical “reservoir” to serve meaningfully as a baseline against which geochemical “anomalies” are evaluated. On the other hand, our findings are consistent with the “Statistical Upper Mantle Assemblage” or “SUMA”-concept, according to which a high level of geochemical heterogeneity is maintained in the upper mantle at all relevant length scales, as a result of the plate-tectonic cycle and intra-mantle processes such as melt-migration and metasomatism.     

Mantle-derived carbon in Hercynian granites. Stable isotopes signatures and C/He associations in the thermomineral waters,N-Portugal

Na–HCO₃–CO₂-rich thermomineral waters issue in the N of Portugal, within the Galicia-Trás-os-Montes region, linked to a major NNE-trending fault, the so-called Penacova-Régua-Verin megalineament. Along this tectonic structure different occurrences of CO₂-rich thermomineral waters are found: Chaves hot waters (67 °C) and also several cold (16.1 °C) CO₂-rich waters. The δ²H and δ¹⁸O values of the thermomineral waters are similar to those of the local meteoric waters. The chemical composition of both hot and cold mineral waters suggests that water–rock reactions are mainly controlled by the amount of dissolved CO₂ (g) rather than by the water temperature. Stable carbon isotope data indicate an external CO₂ inorganic origin for the gas. δ¹³C_CO2 values ranging between ? 7.2‰ and ? 5.1‰ are consistent with a two-component mixture between crustal and mantle-derived CO₂. Such an assumption is supported by the ³He/⁴He ratios measured in the gas phase, are between 0.89 and 2.68 times the atmospheric ratio (Ra). These ratios which are higher than that those expected for a pure crustal origin (≈ 0.02 Ra), indicating that 10 to 30% of the He has originated from the upper mantle. Release of deep-seated fluids having a mantle-derived component in a region without recent volcanic activity indicates that extensive neo-tectonic structures originating during the Alpine Orogeny are still active (i.e., the Chaves Depression).     

Multiphysics modeling of CO2 sequestration in a faulted saline formation in Italy

The present work describes the results of a modeling study addressing the geological sequestration of carbon dioxide (CO₂) in an offshore multi-compartment reservoir located in Italy. The study is part of a large scale project aimed at implementing carbon capture and storage (CCS) technology in a power plant in Italy within the framework of the European Energy Programme for Recovery (EEPR). The processes modeled include multiphase flow and geomechanical effects occurring in the storage formation and the sealing layers, along with near wellbore effects, fault/thrust reactivation and land surface stability, for a CO₂ injection rate of 1 × 10⁶ ton/a. Based on an accurate reproduction of the three-dimensional geological setting of the selected structure, two scenarios are discussed depending on a different distribution of the petrophysical properties of the formation used for injection, namely porosity and permeability. The numerical results help clarify the importance of: (i) facies models at the reservoir scale, properly conditioned on wellbore logs, in assessing the CO₂ storage capacity; (ii) coupled wellbore-reservoir flow in allocating injection fluxes among permeable levels; and (iii) geomechanical processes, especially shear failure, in constraining the sustainable pressure buildup of a faulted reservoir.     

A nitrogen fixation estimate for the Baltic Sea based on continuous pCO2 measurements on a cargo ship and total nitrogen data

Organic matter production and nitrogen fixation in the central Baltic Sea were studied on the basis of high-resolution CO₂ partial pressure data that were obtained from an automated measurement system deployed on a cargo ship. The net organic carbon (OC) production was calculated from a surface water CO₂ mass balance and used to estimate the nitrogen uptake by organic matter during the period March to August 2005. It was shown that the net OC production continued despite the exhaustion of dissolved inorganic nitrogen (DIN) after the spring bloom in April. The nitrogen demand for this production was calculated on the basis of the C/N ratio of organic matter. It was of the same order of magnitude than the winter DIN concentration that fuelled the spring bloom. Since the atmospheric DIN deposition was negligible and no indications of alternative DIN sources were found, it was assumed that N₂ fixation had taken place despite the low temperatures (4–8 °C) in April/May. This “cold fixation” amounted to 74 mmol m^?2 whereas a value of 99 mmol m^?2 was obtained for the summer N₂ fixation during June/July. Due to the contribution of the April/May N₂ fixation, a total annual rate (173±35 mmol m^?2) was obtained for 2005 which is considerably higher than presently accepted estimates. These findings were confirmed by a nitrogen budget based on long-term data (1993–2006) for total nitrogen and total phosphorus concentrations. Furthermore, these data revealed a 30% increase in N₂ fixation during the years 1994–2006.     

Silicate and carbonate melt inclusions associated with diamonds in deeply subducted carbonate rocks

Deeply subducted carbonate rocks from the Kokchetav massif (Northern Kazakhstan) recrystallised within the diamond stability field (P = 4.5–6.0 GPa; T ≈ 1000 °C) and preserve evidence for ultra high-pressure carbonate and silicate melts. The carbonate rocks consist of garnet and K-bearing clinopyroxene embedded in a dolomite or magnesian calcite matrix. Polycrystalline magnesian calcite and polyphase carbonate–silicate inclusions occurring in garnet and clinopyroxene show textural features of former melt inclusions. The trace element composition of such carbonate inclusions is enriched in Ba and light rare earth elements and depleted in heavy rare earth elements with respect to the matrix carbonates providing further evidence that the inclusions represent trapped carbonate melt. Polyphase inclusions in garnet and clinopyroxene within a magnesian calcite marble, consisting mainly of a tight intergrowth of biotite + K-feldspar and biotite + zoisite + titanite, are interpreted to represent two different types of K-rich silicate melts. Both melt types show high contents of large ion lithophile elements but contrasting contents of rare earth elements. The Ca-rich inclusions display high REE contents similar to the carbonate inclusions and show a general trace element characteristic compatible with a hydrous granitic origin. Low SiO₂ content in the silicate melts indicates that they represent residual melts after extensive interaction with carbonates. These observations suggest that hydrous granitic melts derived from the adjacent metapelites reacted with dolomite at ultra high-pressure conditions to form garnet, clinopyroxene – a hydrous carbonate melt – and residual silicate melts. Silicate and carbonate melt inclusions contain diamond, providing evidence that such an interaction promotes diamond growth. The finding of carbonate melts in deeply subducted crust might have important consequences for recycling of trace elements and especially C from the slab to the mantle wedge.