No abstract

While oxidative technologies have been proposed for treatment of waters impacted by aqueous film forming foams (AFFFs), information is lacking regarding the transformation pathways for the chemical precursors to the perfluoroalkyl acids (PFAAs) typically present in such waters. This study examined the oxidative electrochemical treatment of poly- and perfluoroalkyl substances (PFASs) for two AFFF-impacted groundwaters. The bulk pseudo first order rate constant for PFOA removal was 0.23 L h A; for PFOS, this value ranged from 0.084 to 0.23 L h A. Results from the first groundwater studied suggested a transformation pathway where sulfonamide-based PFASs transformed to primarily perfluorinated sulfonamides and perfluorinated carboxylic acids (PFCAs), with subsequent defluorination of the PFCAs. Transient increases in the perfluorinated sulfonamides and PFCAs were observed. For the second groundwater studied, no transient increases in PFAAs were measured, despite the presence of similarly structured suspected PFAA precursors and substantial defluorination. For both waters, suspected precursors were the primary sources of the generated fluoride. Assessment of precursor compound transformation noted the formation of keto-perfluoroalkanesulfonates only in the second groundwater. These results confirm that oxidation and defluorination of suspected PFAA precursors in the second groundwater underwent transformation via a pathway different than that of the first groundwater, which was not captured by total oxidizable precursor assay.

No abstract

Carbon capture and storage is a promising strategy for mitigating the CO(2) contribution to global climate change. The large scale implementation of the technology mandates better understanding of the risks associated with CO(2) injection into geologic formations and the subsequent interactions with groundwater resources. The injected supercritical CO(2) (sc-CO(2)) is a nonpolar solvent that can potentially mobilize organic compounds that exist at residual saturation in the formation. Here, we review the partitioning behavior of selected organic compounds typically found in depleted oil reservoirs in the residual oil-brine-sc-CO(2) system under carbon storage conditions. The solubility of pure phase organic compounds in sc-CO(2) and partitioning of organic compounds between water and sc-CO(2) follow trends predicted based on thermodynamics. Compounds with high volatility and low aqueous solubility have the highest potential to partition to sc-CO(2). The partitioning of low volatility compounds to sc-CO(2) can be enhanced by cosolvency due to the presence of higher volatility compounds in the sc-CO(2). The effect of temperature, pressure, salinity, pH, and dissolution of water molecules into sc-CO(2) on the partitioning behavior of organic compounds in the residual oil-brine-sc-CO(2) system is discussed. Data gaps and research needs for models to predict the partitioning of organic compounds in brines and from complex mixtures of oils are presented. Models need to be able to better incorporate the effect of salinity and cosolvency, which will require more experimental data from key classes of organic compounds.