Experimental analysis and modeling of perfluorocarbon transport in the vadose zone : implications for monitoring CO₂ leakage at CCS sites

Perfluorocarbon tracers (PFTs) are commonly proposed tracers for use in carbon capture and sequestration (CCS) leak detection and vadose zone monitoring programs. Tracers are co-injected with supercritical CO₂ and monitored in the vadose zone to identify leakage and calculate leakage rates. These calculations assume PFTs exhibit “ideal” tracer behavior (i.e. do not sorb onto or react with porous media, partition into liquid phases or undergo decay). This assumption has been brought into question by lab and field evaluations showing PFT partitioning into soil contaminants and sorbing onto clay. The objective of this study is to identify substrates in which PFTs behave conservatively and quantify non-conservative behavior. PFT breakthrough curves are compared to those of a second, conservative tracer, sulfur hexafluoride (SF₆). Breakthrough curves are generated in 1D flow-through columns packed with 5 different substrates: silica beads, quartz sand, illite, organic-rich soil, and organic-poor soil. Constant flow rate of carrier gas, N₂, is maintained. A known mass of tracer is injected at the head of the columns and the effluent analyzed at regular intervals for tracers at picogram levels by gas chromatography. PFT is expected to behave conservatively with respect to SF₆ in silica beads or quartz sand and non-conservatively in columns with clay or organics. However, results demonstrate PFT retardation with respect to SF₆ in all media (retardation factor is 1.1 in silica beads and quartz sand, 2.5 in organic-rich soil, >20 in organic-poor soil, and >100 in illite). Retardation is most likely due to sorption onto clays and soil organic matter or condensation to the liquid phase. Sorption onto clays appears to be the most significant factor. Experimental data are consistent with an analytical advection/diffusion model. These results show that PFT retardation in the vadose zone has not been adequately considered for interpretation of PFT data for CCS monitoring. These results are preliminary and do not take into account more realistic vadose zone conditions such as the presence of water, in which PFTs are insoluble. Increased moisture content will likely decrease sorption onto porous media and retardation in the vadose zone may be less than determined in these experiments.