An approach to the geochemical modelling of water-rock interaction in CO2 storage geological reservoirs: the Weyburn Project (Canada) case study

Geological storage is one of the most promising technologies for reducing anthropogenic atmospheric emissions of CO2. Among the several CO2 storage techniques, sequestration in deep-seated saline aquifers implies four processes: a) supercritical fluid into geologic structure (physical trapping), b) dissolved CO2(aq) due to very long flow path (hydrodynamic trapping), c) dissolved CO2(aq) (solubility trapping), and d) secondary carbonates (mineral trapping). The appealing concept that CO2 can permanently be retained underground has prompted several experimental studies in Europe and North America sponsored by IEA GHG R&D, EU and numerous international industrials and governments, the most important project being the International Energy Agency Weyburn CO2 Monitoring & Storage, an EnCana’s CO2 injection EOR project at Weyburn (Saskatchewan, Canada). Owing to the possible risks associated to this technique, numerical modelling procedures of geochemical processes are necessary to investigate the short- to long-term consequences of CO2 storage. Assumptions and gap-acceptance are made to reconstruct the reservoir conditions (pressure, pH, chemistry, and mineral assemblage), although most strategic geochemical parameters of deep fluids are computed by a posteriori procedure due to the sampling collection at the wellhead, i.e. using depressurised aliquots. In this work a new approach to geochemical model capable of to reconstruct the reservoir chemical composition (T, P, boundary conditions and pH) is proposed using surface analytical data to simulate the short-medium term reservoir evolution during and after the CO2 injection. The PRHEEQC (V2.11) Software Package via thermodynamic corrections to the code default database has been used to obtain a more realistic modelling. The main modifications brought about the Software Package are: i) addition of new solid phases, ii) use of P>0.1 Mpa, iii) variation of the CO2 supercritical fugacity and solubility under reservoir conditions, iv) addition of kinetic rate equations of several minerals and v) calculation of reaction surface area. The Weyburn Project was selected as case study to test our model. The Weyburn oil-pull is recovered from the Midale Beds (1300-1500 m deep) that consist of two units of Mississippian shallow marine carbonate-evaporites: i) the dolomitic “Marly” and ii) the underlying calcitic “Vuggy”, sealed by an anhydrite cap-rock. About 3 billions mc of supercritical CO2 have been injected into the “Phase A1” injection area. The INGV and the University of Calgary (Canada), have carried out a geochemical monitoring program (ca. thrice yearly- from pre-injection trip: “Baseline” trip, August 2000, to September 2004). The merged experimental data are the base of the present geochemical modeling. On the basis of the available data, i.e. a) bulk mineralogy of the Marly and Vuggy reservoirs; b) mean gas-cap composition at the wellheads and c) selected pre- and post-CO2 injection water samples, the in-situ (62 °C and 0.1 MPa) reservoir chemical composition (including pH and the boundary conditions as PCO2, PH2S) has been re-built by the chemical equilibrium among the various phases, minimizing the effects of the past 30-years of water flooding in the oil field. The kinetic evolution of the CO2-rich Weyburn brines interacting with the host-rock minerals performed over 100 years after injection have also been computed. The reaction path modeling suggests that CO2 can mainly be neutralized by solubility and mineral trapping via Dawsonite precipitation. To validate our model the geochemical impact of three years of CO2 injection (September 2000-2003) has been simulated by kinetically controlled reactions. The calculated chemical composition after the CO2 injection is consistent with the analytical data of samples collected in 2003 with a <5 % error for most analytical species, with the exception of Ca and Mg (error >90%), likely due to the complexation effect of carboxilic acid

Spatial distribution of arsenic, uranium and vanadium in the volcanic-sedimentary aquifers of the Vicano–Cimino Volcanic District (Central Italy)

Arsenic concentrations were analysed for 328 water samples collected in the Vicano–Cimino Volcanic District (VCVD), an areawhere severe contamination of groundwater has become a serious problemfollowing the recent application of the EU Directive on the maximum allowable concentration level for As in drinking waters. In addition, uranium and vanadium concentrations were also analysed in light of the enhanced interest on their environmental toxicity. Waters were collected from springs and wells fed by cold and shallow volcanic–sedimentary aquifers, which locally represent the main drinking water source. Thermal springs (≤63 °C) related to an active hydrothermal reservoir and waters associated with a CO2-rich gas phase of deep provenance were also analysed. The collected data showed that the As concentrations in the shallow aquifers varied in a wide range (0.05–300 μg/L) and were primarily controlled by water–rock interaction processes. High As concentrations (up to 300 μg/L) were measured in springs and wells discharging from the volcanic products, and about 66% exceeded the limit of 10 μg/L for drinkingwaters,whereaswaters circulatingwithin the sedimentary formations displayed much lower values (0.05–13 μg/L; ~4% exceeding the threshold limit). Thermal waters showed the highest As concentrations (up to 610 μg/L) as the result of the enhanced solubility of As-rich volcanic rocks during water–rock interaction processes at high temperatures. Where the local structural setting favoured the rise of fluids from the deep hydrothermal reservoir and their interaction with the shallow volcanic aquifer, relatively higher concentrations were found. Moreover, well overexploitation likely caused the lateral inflow of As-rich waters towards not contaminated areas. Uraniumand vanadiumconcentrations ofwaters circulating in the volcanic rocks ranged from0.01 to 85 μg/L and 0.05 to 62 μg/L, respectively. Less than 2% of analysed samples exceeded theWorld Health Organization's provisional guidelines for U (30 μg/L), while none of them was above the Italian limit value of V in drinking water (120 μg/L). Lower U (0.07–22 μg/L and 0.02–13 μg/L, respectively) and V concentrations (0.05–24 μg/L and 0.18–17 μg/L, respectively) were measured in the water samples from the sedimentary aquifer and thermal waters. Local lithology appeared as the main factor affecting the U and V contents in the shallow aquifers, due to the high concentrations of these two elements in the volcanic formations when compared to the sedimentary units. In addition, high U concentrations were found in correspondence with U mineralization occurring within the VCVD, fromwhich U is released in solution mainly through supergene oxidative alteration. Redox conditions seem to play amajor role in controlling the concentrations of U and V inwaters. Oxidizing conditions characterizing the cold waters favour the formation of soluble U- and V-species, whereas thermal waters under anoxic conditions are dominated by relatively insoluble species. Geostatistical techniques were used to draw contour maps by using variogram models and kriging estimation aimed to define the areas of potential health risk characterized by As, U and V-rich waters, thus providing a useful tool for water management in a naturally contaminated area to local Authorities

Active real-time analyzers vs. passive/diffusive samplers for hydrogen sulfide (H2S) in air: a critical comparison

Hydrogen sulfide (H2S) is a gas pollutant discharged in air from a large number of natural and anthropogenic sources. Its peculiar rotten-egg smell, causing odor nuisance to neighboring communities, is detectable at concentrations between 0.7 and 42 μg/m3 (Schiffman &amp; Williams, 2005). High H2S concentrations could cause eye irritation, damage to the upper respiratory apparatus and loss of smell. The effects of long-term low level (&lt; 2,800 μg/m3) exposures to H2S are still matter of debate (Bates et al., 2013). Hence, the development of techniques for accurate measurements of H2S in air at a wide range of concentrations is a primary issue in environmental monitoring. Two different approaches are currently used: 1) passive samplers and 2) real-time measurements. The latter are generally expensive and require a power supply. On the contrary, passive samplers are low cost and can be deployed in the field with minimal maintenance. Therefore, passive samplers offer an appealing alternative to real-time measurements, especially for regional-scale monitoring. However, the reliability of passive samplers in outdoor applications strongly depends on several environmental factors, such as temperature, humidity and wind speed (Delgado-Saborit &amp; Esteve-Cano, 2006). In this study a comparison between H2S measurements using diffusive radial-type passive samplers (Radiello) and a real-time gas analyzer (Thermo Scientific Model 450i) based on pulsed fluorescence, is presented. The measurements were carried out in areas affected by both anthropogenic and natural sources using both techniques. The results show substantial differences. The passive samplers systematically produce higher H2S concentrations than those of the active analyzer. The relative error was up to &gt; 1,000% for concentrations &lt; 7 μg/m3 and exposure duration ≥ 2 hours. H2S measurements by Radiello were affected by meteo parameters (wind, rain, humidity, temperature). The efficiency of this method was demonstrated to be also strongly dependent on H2S concentrations. In addition, passive samplers give an average concentration value for the exposure period, but are not able to detect short-term H2S increments. These results show that the use of passive samplers for environmental monitoring should thus be limited to preliminary largescale semi-quantitative assessment. A reliable study on the dispersion dynamics of contaminants in air cannot exclude the acquisition of high-frequency data through active analyzers

BARRIER EFFECT IN CO2 CAPTURE AND STORAGE FEASIBILITY STUDY

CO2 Capture & Storage (CCS) in saline aquifer is one of the most promising technologies for reducing anthropogenic emission of CO2. Feasibility studies for CO2 geo-sequestration in Italy have increased in the last few years. Before planning a CCS plant an appropriate precision and accuracy in the prediction of the reservoir evolution during injection, in terms of both geochemical calculation and fluid flow properties, is demanded. In this work a geochemical model will be presented for an offshore well in the Tyrrhenian Sea where the injection of 1.5 million ton/year of CO2 is planned. The dimension of the trapping structure requires to study an area of about 100 km2 and 4 km deep. Consequently, three different simulations were performed by means of TOUGHREACT code with Equation Of State module ECO2N. The first simulation is a stratigraphic column with a size of 110*110*4,000 meters and a metric resolution in the injection/cap-rock area (total of 8,470 elements), performed in order to asses the geochemical evolution of the cap-rock and to ensure the sealing of the system. The second simulation is at large scale in order to assess the CO2 path from the injection towards the spill point (total of about 154,000 elements). During this simulation, the effect of the full coupling of chemistry with fluid flow and a relevant effect in the expected CO2 diffusion velocity was recognized. Owing to the effect of chemical reaction and coupling terms (porosity/permeability variation with mineral dissolution/precipitation), the diffusion velocity results to be 20% slower than in a pure fluid flow simulation. In order to give a better picture of this 'barrier' effect, where the diffusion of the CO2-rich acidic water into the carbonate reservoir originates a complex precipitation/dissolution area, a small volume simulation with a 0.1 m grid was elapsed. This effect may potentially i) have a big impact on CO2 sequestration due to the reduction of available storage volume reached by the CO2 plume in 20 years and/or the enhanced injection pressure and ii) outline the relevance of a full geochemical simulation in an accurate prediction of the reservoir properties

Overview of the geochemical modeling on CO2 capture & storage in Italian feasibility studies

CO2 Capture & Storage in saline aquifers is presently one of the most promising technologies for reducing anthropogenic emissions of CO2. In these sites the short-longterm consequences of CO2 storage into a deep reservoir can be predicted by numerical modelling of geochemical processes. Unfortunately a common problem working with off-shore closed wells, where only the well-log information are available, is to obtain physico-chemical data (e.g. petrophysical and mineralogical) needed to reliable numerical simulations. Available site-specific data generally include only basic physical parameters such as temperature, pressure, and salinity of the formation waters. In this study we present a methodological procedure that allows to estimate and integrate lacking information to geochemical modelling of deep reservoirs such as: i) bulk and modal mineralogical composition, ii) porosity and permeability of the rock obtained from heat flow measurements and temperature, iii) chemical composition of formation waters (at reservoir conditions) prior of CO2 injection starting from sampling of analogue outcropping rock formations. The data sets in this way reconstructed constitute the base of geochemical simulations applied on some deep-seated Italian carbonatic and sandy saline aquifers potentially suitable for geological CO2 storage. Numerical simulations of reactive transport has been performed by using the reactive transport code TOUGHREACT via pressure corrections to the default thermodynamic database to obtain a more realistic modelling. Preliminary results of geochemical trapping (solubility and mineral trapping) potentiality and cap-rock stability as strategic need for some feasibility studies near to be started in Italy are here presented and discussed

A new geochemical approach to estimate the distribution of air pollutants from natural and anthropogenic sources: examples from Solfatara Crater (Campi Flegrei, Southern Italy) and Mt. Amiata Volcano (Siena, Central Italy)

Volcanic and geothermal systems significantly contribute to the input of volatile contaminants, such as mercury and hydrogen sulfide, into the atmosphere. Mercury has a strong environmental impact. In the atmosphere the prevalent elemental form is Hg0 (~98 %), whose main physical-chemical features are: high volatility, low solubility and chemical inertness. Hydrogen sulfide (H2S), one of the most abundant gas compounds in volcanic fluids, is highly poisoning and corrosive and unpleasantly smells of rotten eggs. Measurements of Hg0 and H2S concentrations in air are commonly performed by means of passive samplers. However, real-time measurements, coupled with monitoring of local atmospheric conditions, are strongly recommended for a reliable reconstruction of the dispersion dynamics once such contaminants are discharged in air. In this paper, a new real-time measurement method for Hg0 and H2S is presented. A portable Zeeman atomic absorption spectrometer with high frequency modulation of light polarization (Lumex RA-915M) and a pulsed fluorescence gas analyzer (Thermo Scientific Model 450i) were used for Hg0 and H2S measurements, respectively. These instruments were synchronized and set to high-frequency acquisition. Measurements were carried out along transects at an average speed &lt;10 km/h. GPS data and meteorological parameters (wind direction and intensity) were also recorded. The proposed method was applied in two different sites, characterized by natural (Solfatara Crater, Campi Flegrei, Southern Italy) and anthropogenic (Mt. Amiata Volcano, Siena, Central Italy) emissions. With this highly efficient and effective approach, a reliable and reproducible Hg0 and H2S distribution in air was provided, allowing to identify and characterize the gas sources from such different environments. At Solfatara, the distribution of Hg0 and H2S concentrations, the highest values being measured close to the fumarolized areas (&gt;60 ng/m3 and &gt;2,100 μg/m3, respectively), suggests that these gases were discharged from both fumaroles and diffuse degassing from the crater bottom. At Mt. Amiata, the maximum Hg0 and H2S concentrations (&gt;100 ng/m3 and &gt;35 μg/m3, respectively) were recorded close to the geothermal power plants of Piancastagnaio. According to detailed dot-maps constructed on the basis of the measured values, as expected, wind was the main environmental parameter able to control the behavior and the dispersion halo of the Hg0- and H2S-rich plumes emitted from the contaminant sources

Fluid geochemistry and seismic activityin the period 1998-2002 at Turrialba Volcano (Costa Rica)

Turrialba Volcano, located in Central-Southern Costa Rica, has been characterized, since the last period of eruptive activity in 1884-1886, by a weak and discontinuous fumarolic activity in the western area of its summit. During the 1998-2002 period, fumaroles discharging from central and West craters were collected for chemical analyses of major and trace gas compounds, 13C/12C in CO2 and 18O/16O and D/H (in one fumarolic condensate), isotopic ratios. Geophysical measurements (seismic activity and ground deformation), monitored in the same period, were compared to geochemical data to define the status of the volcanic system. Chemical and isotopic characteristics of fumaroles of Turrialba Volcano seem to be related to interaction processes between a magmatic source and a shallower hydrothermal aquifer. Since February 1997, seismicity at Turrialba Volcano gradually increased, while since August 2001 new fumaroles start to discharge from a new fracture system located in the area between central and West craters. Since September 2001, strong compositional changes of gas discharges have been recorded at central crater. These occurrences are possibly due to variations in the permeability of the conduit system feeding the fumaroles. Heat pulse episodes from a magmatic source have possibly caused the increase of vapour pressure at depth and, consequently, favoured the uprising of the magmatic fluids toward the surface. The observed evolution of chemical and physical parameters suggests that to forecast a possible renewal of the volcanic activity in the near future a full program of both geochemical and geophysical surveillance must be provided at Turrialba Volcano