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Authors: Cantucci, B.* 
Procesi, M.* 
Buttinelli, M.* 
Montegrossi, G.* 
Vaselli, O.* 
Quattrocchi, F.* 
Title: Mineralogy and geochemical trapping of CO2 in an Italian carbonatic deep saline aquifer: preliminary results
Issue Date: 18-Apr-2008
Keywords: CO2 storage
Geochemical modeling
Subject Classification01. Atmosphere::01.01. Atmosphere::01.01.02. Climate 
01. Atmosphere::01.01. Atmosphere::01.01.06. Thermodynamics 
03. Hydrosphere::03.01. General::03.01.01. Analytical and numerical modeling 
03. Hydrosphere::03.02. Hydrology::03.02.03. Groundwater processes 
03. Hydrosphere::03.04. Chemical and biological::03.04.03. Chemistry of waters 
04. Solid Earth::04.02. Exploration geophysics::04.02.01. Geochemical exploration 
04. Solid Earth::04.04. Geology::04.04.12. Fluid Geochemistry 
Abstract: CO2 Capture & Storage (CCS) is presently one of the most promising technologies for reducing anthropogenic emissions of CO2 . Among the several potential geologi- cal CO2 storage sites, e.g. depleted oil and gas field, unexploitable coal beds, saline aquifers, the latter are estimated to have the highest potential capacity (350-1000 Gt CO2 ) and, being relatively common worldwide, a higher probability to be located close to major CO2 anthropogenic sources. In these sites CO2 can safely be retained at depth for long times, as follows: a) physical trapping into geologic structures; b) hy- drodynamic trapping where CO2(aq) slowly migrates in an aquifer, c) solubility trap- ping after the dissolution of CO2(aq) and d) mineral trapping as secondary carbon- ates precipitate. Despite the potential advantages of CO2 geo-sequestration, risks of CO2 leakage from the reservoir have to be carefully evaluated by both monitoring techniques and numerical modeling used in “CO2 analogues”, although seepage from saline aquifers is unlikely to be occurring. The fate of CO2 once injected into a saline aquifer can be predicted by means of numerical modelling procedures of geochemical processes, these theoretical calculations being one of the few approaches for inves- tigating the short-long-term consequences of CO2 storage. This study is focused on some Italian deep-seated (>800 m) saline aquifers by assessing solubility and min- eral trapping potentiality as strategic need for some feasibility studies that are about to be started in Italy. Preliminary results obtained by numerical simulations of a geo- chemical modeling applied to an off-shore Italian carbonatic saline aquifer potential suitable to geological CO2 storage are here presented and discussed. Deep well data, still covered by industrial confidentiality, show that the saline aquifer, includes six Late Triassic-Early Jurassic carbonatic formations at the depth of 2500-3700 m b.s.l. These formations, belonging to Tuscan Nappe, consist of porous limestones (mainly calcite) and marly limestones sealed, on the top, by an effective and thick cap-rock (around 2500 m) of clay flysch belonging to the Liguride Units. The evaluation of the potential geochemical impact of CO2 storage and the quantification of water-gas-rock reactions (solubility and mineral trapping) of injection reservoir have been performed by the PRHEEQC (V2.11) Software Package via corrections to the code default ther- modynamic database to obtain a more realistic modelling. The main modifications to the Software Package are, as follows: i) addition of new solid phases, ii) variation of the CO2 supercritical fugacity and solubility under reservoir conditions, iii) addi- tion of kinetic rate equations of several minerals and iv) calculation of reaction sur- face area. Available site-specific data include only basic physical parameters such as temperature, pressure, and salinity of the formation waters. Rocks sampling of each considered formation in the contiguous in-shore zones was carried out. Mineralogy was determined by X-Ray diffraction analysis and Scanning Electronic Microscopy on thin sections. As chemical composition of the aquifer pore water is unknown, this has been inferred by batch modeling assuming thermodynamic equilibrium between minerals and a NaCl equivalent brine at reservoir conditions (up to 135 ̊C and 251 atm). Kinetic modelling was carried out for isothermal conditions (135 ̊C), under a CO2 injection constant pressure of 251 atm, between: a) bulk mineralogy of the six formations constituting the aquifer, and b) pre-CO2 injection water. The kinetic evolu- tion of the CO2 -rich brines interacting with the host-rock minerals performed over 100 years after injection suggests that solubility trapping is prevailing in this early stage of CO2 injection. Further and detailed multidisciplinary studies on rock properties, geochemical and micro seismic monitoring and 3D reservoir simulation are necessary to better characterize the potential storage site and asses the CO2 storage capacity.
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