Limitations for brine acidification due to SO₂ co-injection in geologic carbon sequestration

Co-injection of sulfur dioxide during geologic carbon sequestration can cause enhanced brine acidification. The magnitude and timescale of this acidification will depend, in part, on the reactions that control acid production and on the extent and rate of SO₂ dissolution from the injected CO₂ phase. Here, brine pH changes were predicted for three possible SO₂ reactions: hydrolysis, oxidation, or disproportionation. Also, three different model scenarios were considered, including models that account for diffusion-limited release of SO₂ from the CO₂ phase. In order to predict the most extreme acidification potential, mineral buffering reactions were not modeled. Predictions were compared to the case of CO₂ alone which would cause a brine pH of 4.6 under typical pressure, temperature, and alkalinity conditions in an injection formation. In the unrealistic model scenario of SO₂ phase equilibrium between the CO₂ and brine phases, co-injection of 1% SO₂ is predicted to lead to a pH close to 1 with SO₂ oxidation or disproportionation, and close to 2 with SO₂ hydrolysis. For a scenario in which SO₂ dissolution is diffusion-limited and SO₂ is uniformly distributed in a slowly advecting brine phase, SO₂ oxidation would lead to pH values near 2.5 but not until almost 400 years after injection. In this scenario, SO₂ hydrolysis would lead to pH values only slightly less than those due to CO₂ alone. When SO₂ transport is limited by diffusion in both phases, enhanced brine acidification occurs in a zone extending only 5 m proximal to the CO₂ plume, and the effect is even less if the only possible reaction is SO₂ hydrolysis. In conclusion, the extent to which co-injected SO₂ can impact brine acidity is limited by diffusion-limited dissolution from the CO₂ phase, and may also be limited by the availability of oxidants to produce sulfuric acid.