Monitoring permanent CO2 storage by in situ mineral carbonation using a reactive tracer technique

AbstractIn situ mineral carbonation provides the most effective and permanent solution for geologic CO2 storage. Basaltic rocks have the potential to store large volumes of CO2 as (Ca, Mg, Fe) carbonates [1]. Existing monitoring and verification techniques for geologic CO2 storage are insufficient to quantitatively characterize solubility and mineral trapping in a geologic reservoir. We developed and tested a new reactive tracer technique for quantitative monitoring and detection of dissolved and chemically transformed CO2. The technique involves the active tagging of the injected CO2 with low levels of radiocarbon (14C) as a reactive tracer in combination with the injection of non-reactive tracers such as sulfurhexafluoride (SF6) and trifluoromethylsulphur pentafluoride (SF5CF3). The tracer technique has been applied at the CarbFix pilot injection site in Hellisheidi, Iceland as part of a comprehensive geochemical monitoring program during two injection phases; Phase III and IV. SF6 and SF5CF3 confirm the arrival of the injected CO2 and CO2+H2S solutions at the first observation well HN04, which is 125m west of the injection well at 520 m depth. The initial breakthrough of the migrating dissolved CO2 front occurred 63 and 62 days after injection began as evidenced by an initial peak in the SF6, SF5CF3, 14C, and dissolved inorganic carbon (DIC) concentrations. The major increase in the non-reactive tracer concentrations occurred several months after the initial breakthrough, although no major concentration increase has been observed for 14C and DIC suggesting that mineral reactions are dominant during CO2 injection

Rapid solubility and mineral storage of CO2 in basalt

The long-term security of geologic carbon storage is critical to its success and public acceptance. Much of the security risk associated with geological carbon storage stems from its buoyancy. Gaseous and supercritical CO2 are less dense than formation waters, providing a driving force for it to escape back to the surface. This buoyancy can be eliminated by the dissolution of CO2 into water prior to, or during its injection into the subsurface. The dissolution makes it possible to inject into fractured rocks and further enhance mineral storage of CO2 especially if injected into silicate rocks rich in divalent metal cations such as basalts and ultra-mafic rocks. We have demonstrated the dissolution of CO2 into water during its injection into basalt leading to its geologic solubility storage in less than five minutes and potential geologic mineral storage within few years after injection [1–3]. The storage potential of CO2 within basaltic rocks is enormous. All the carbon released from burning of all fossil fuel on Earth, 5000 GtC, can theoretically be stored in basaltic rocks [4]

Gas exchange measurements in natural systems

Direct knowledge of the rates of gas exchange in lakes and the ocean is based almost entirely on measurements of the isotopes /sup 14/C, /sup 222/Rn and /sup 3/He. The distribution of natural radiocarbon has yielded the average rate of CO/sub 2/ exchange for the ocean and for several closed basin lakes. That of bomb produced radiocarbon has been used in the same systems. The /sup 222/Rn to /sup 226/Ra ratio in open ocean surface water has been used to give local short term gas exchange rates. The radon method generally cannot be used in lakes, rivers, estuaries or shelf areas because of the input of radon from sediments. A few attempts have been made to use the excess /sup 3/He produced by decay of bomb produced tritium in lakes to give gas transfer rates. The uncertainty in the molecular diffusivity of helium and in the diffusivity dependence of the rate of gas transfer holds back the application of this method. A few attempts have been made to enrich the surface waters of small lakes with /sup 226/Ra and /sup 3/H in order to allow the use of the /sup 222/Rn and /sup 3/He methods. While these studies give broadly concordant results, many questions remain unanswered. The wind velocity dependence of gas exchange rate has yet to be established in field studies. The dependence of gas exchange rate on molecular diffusivity also remains in limbo. Finally, the degree of enhancement of CO/sub 2/ exchange through chemical reactions has been only partially explored. 49 references, 2 figures, 2 tables

Steady-state and transient modeling of tracer and nutrient distributions in the global ocean

The deep circulation model developed by Wright and Stocker has been used to represent the latitude-depth distributions of temperature, salinity, radiocarbon and color'' tracers in the Pacific, Atlantic and Indian Oceans. Restoring temperature and salinity to observed surface data the model shows a global thermohaline circulation where deep water is formed in the North Atlantic and in the Southern Ocean. A parameter study reveals that the high-latitude surface salinity determines the composition of deep water and its flow in the global ocean. Increasing Southern Ocean surface salinity by 0.4 ppt the circulation changes from a present-day mode where North Atlantic Deep Water is one where Antarctic Bottom Water is dominant. An inorganic carbon cycle with surface carbonate chemistry is included, and gas exchange is parameterized in terms of pCO{sub 2} differences. Pre- industrial conditions are achieved by adjusting the basin-mean alkalinity. A classical 2{times}CO{sub 2} experiment yields the intrinsic time scales for carbon uptake of the ocean; they agree with those obtained from simple box models or 3-dimensional ocean general circulation models. Using the estimated industrial anthropogenic input of CO{sub 2} into the atmosphere the model requires, consistent with other model studies, an additional carbon flux to match the observed increase of atmospheric pCO{sub 2}. We use more realistic surface boundary conditions which reduce sensitivity to freshwater discharges into the ocean. In a glacial-to-interglacial experiment rapid transitions of the deep circulation between two different states occur in conjunction with a severe reduction of the meridional heat flux and sea surface temperature during peak melting. After the melting the conveyor belt circulation restarts

Steady-state and transient modeling of tracer and nutrient distributions in the global ocean

The balance of stable and decaying tracers was incorporated into a latitude-depth ocean circulation model which resolves the major ocean basin and is coupled to an atmospheric energy balance model. The modern distribution of radiocarbon and the analysis of artificial color tracers enabled the census of the deep water masses. We show that good agreement with the observation can be achieved if the surface forcing is modified. The same process could also account for long-term, large-scale changes of the global thermohaline circulation. Uptake rates of carbon are investigated using an inorganic carbon cycle model and performing 2 [times] CO[sub 2]-experiments. We prescribe the industrial evolution of pCO[sub 2] in the atmosphere from 1792 to 1988 and calculate the total flux of carbon into the world ocean. Results are in good agreement with two recent 3-dimensional model simulation. First results using an organic carbon cycle in this model are presented. Changes in the hydrological cycle can stabilize the thermohaline circulation in the Atlantic and enable simulation of climate events resembling the Younger Dryas. By adding the balance of radiocarbon the evolution of its atmospheric concentration is studied during rapid changes of deep ocean ventilation. A resumption of ventilation creates a rapid decrease of atmospheric radiocarbon which is able to mask the natural decay