Interpretation of Perfluorocarbon Tracer Data Collected During the Frio Carbon Dioxide Sequestration Test

In October of 2004 over 1600 tons of CO2 was injected into a brine-bearing sandstone unit within the Frio Formation. An injection well was used to introduce the CO2 into the Frio at a depth of 1540 meters below the surface. A monitoring well located 31 meters updip from the injection well was used to sample formation fluids and detect the breakthrough of the CO2 plume. Perfluorocarbon tracers (PFTs) were injected in three paired intervals at the beginning and middle of the CO2 injection. The four PFTs selected for injection were perfluoromethylcyclopentane (PMCP), perfluoromethylcyclohexane (PMCH), perfluorodimethylcyclohexane (PDCH), and perfluorotrimethylcyclohexane (PTCH). The PFTs were used as a means to monitor CO2 plume breakthroughs and aid in the interpretation of CO2 flow path development. Fluid samples were collected at the monitoring well during and after the CO2 and PFT injections. These samples were later analyzed in the laboratory to measure the concentration of PFTs. Laboratory analysis was performed using a gas chromatograph (GC) equipped with an electron capture detector (ECD). Standardization of the data set was achieved by dividing C by Cno (C/Cno), where C is the molar mass of PFT and CO2 recovered and Cno is the initial molar mass of PFT and CO2 injected. The C/Cno data showed the amount of PFT dilution that occurred between injection and collection. Analysis of the C/Cno data revealed three breakthrough peaks corresponding with the three PFT injections at 54, 157, and 173 hours after the start of CO2 injection, with an average travel time of 51 hours for each injection. With each subsequent PFT peak a greater amount of PFT dilution was observed along with a broadening of the breakthrough peak. The first PFT breakthrough spans 10 hours, the second spans 20 hours and the third spans 24 hours. The increase in peak broadness observed in each subsequent breakthrough may have been caused by increased CO2 saturation. Since PFTs are more soluble in CO2 than in water, their dilution could indicate that additional CO2 dispersed the injected PFTs. Additionally, further flow path development could also lead to broader PFT breakthrough peaks. Therefore, the C/Cno data shows that the travel time for each of the PFT injections was similar (~51 hours), but broadening of the peaks may represent increased CO2 saturation or further developing flow paths.