Electrochemical Transformations of Perfluoroalkyl Acid (PFAA) Precursors and PFAAs in Groundwater Impacted with Aqueous Film Forming Foams.

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-1 A-1; for PFOS, this value ranged from 0.084 to 0.23 L h-1 A-1. 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.

Trace organic contaminants in urban runoff: Associations with urban land-use.

Urban development has led to an increase in urban runoff, accompanied with a decrease in water quality during rain events. One of the major causes of the decrease in water quality is the presence of trace organic contaminants in urban runoff. However, little is known about the sources of organic contaminants in urban runoff, especially related to land-use and temporal trends in those associated land uses. The objective of this study was to assess the occurrence and concentration trends of organic contaminants for a high-density residential site and commercial strip site in Madison, WI. Flow-weighted samples of urban stormwater runoff, collected with an auto-sampler, were composited and analyzed, producing mean organic contaminants concentrations for each storm event. The contaminants, which include pesticides, flame retardants, polycyclic aromatic hydrocarbons, corrosion inhibitors, among others, were extracted and analyzed by gas chromatography coupled with mass spectrometry or liquid chromatography coupled with tandem mass spectrometry. There were 30 organic contaminants that had greater than 50% detections in at least one of the sites, and those organic contaminants did provide information on similarities and differences of organic contaminants in urban runoff derived from different land uses. The sum of the total measured pesticides showed no significant difference between sites; this was likely due to the considerable green space and associated pesticide use in both sites. However, there were higher total concentrations of organophosphate flame retardants and corrosion inhibitors in the residential site. The reason for this is unknown and will require follow-up studies; however, several hypotheses are presented. Conversely, there were higher total concentrations of polycyclic aromatic hydrocarbons in the commercial site; this is most likely due to higher vehicle traffic in the commercial site. These data show that land-use may be important in determining the composition and concentrations of trace organic contaminants in urban stormwater runoff.

Measurement and Modeling of Setschenow Constants for Selected Hydrophilic Compounds in NaCl and CaCl2 Simulated Carbon Storage Brines.

Carbon capture, utilization, and storage (CCUS), a climate change mitigation strategy, along with unconventional oil and gas extraction, generates enormous volumes of produced water containing high salt concentrations and a litany of organic compounds. Understanding the aqueous solubility of organic compounds related to these operations is important for water treatment and reuse alternatives, as well as risk assessment purposes. The well-established Setschenow equation can be used to determine the effect of salts on aqueous solubility. However, there is a lack of reported Setschenow constants, especially for polar organic compounds. In this study, the Setschenow constants for selected hydrophilic organic compounds were experimentally determined, and linear free energy models for predicting the Setschenow constant of organic chemicals in concentrated brines were developed. Solid phase microextraction was employed to measure the salting-out behavior of six selected hydrophilic compounds up to 5 M NaCl and 2 M CaCl2 and in Na-Ca-Cl brines. All compounds, which include phenol, p-cresol, hydroquinone, pyrrole, hexanoic acid, and 9-hydroxyfluorene, exhibited log-linear behavior up to these concentrations, meaning Setschenow constants previously measured at low salt concentrations can be extrapolated up to high salt concentrations for hydrophilic compounds. Setschenow constants measured in NaCl and CaCl2 brines are additive for the compounds measured here; meaning Setschenow constants measured in single salt solutions can be used in multiple salt solutions. The hydrophilic compounds in this study were selected to elucidate differences in salting-out behavior based on their chemical structure. Using data from this study, as well as literature data, linear free energy relationships (LFERs) for prediction of NaCl, CaCl2, LiCl, and NaBr Setschenow constants were developed and validated. Two LFERs were improved. One LFER uses the Abraham solvation parameters, which include the index of refraction of the organic compound, organic compound's polarizability, hydrogen bonding acidity and basicity of the organic compound, and the molar volume of the compound. The other uses an octanol-water partitioning coefficient to predict NaCl Setschenow constants. Improved models from this study now include organic compounds that are structurally and chemically more diverse than the previous models. The CaCl2, LiCl, and NaBr single parameter LFERs use concepts from the Hofmeister series to predict new, respective Setschenow constants from NaCl Setschenow constants. The Setschenow constants determined here, as well as the LFERs developed, can be incorporated into CCUS reactive transport models to predict aqueous solubility and partitioning coefficients of organic compounds. This work also has implications for beneficial reuse of water from CCUS; this can aide in determining treatment technologies for produced waters.

New Linear Partitioning Models Based on Experimental Water: Supercritical CO2 Partitioning Data of Selected Organic Compounds.

Partitioning coefficients of organic compounds between water and supercritical CO2 (sc-CO2) are necessary to assess the risk of migration of these chemicals from subsurface CO2 storage sites. Despite the large number of potential organic contaminants, the current data set of published water-sc-CO2 partitioning coefficients is very limited. Here, the partitioning coefficients of thiophene, pyrrole, and anisole were measured in situ over a range of temperatures and pressures using a novel pressurized batch-reactor system with dual spectroscopic detectors: a near-infrared spectrometer for measuring the organic analyte in the CO2 phase and a UV detector for quantifying the analyte in the aqueous phase. Our measured partitioning coefficients followed expected trends based on volatility and aqueous solubility. The partitioning coefficients and literature data were then used to update a published poly parameter linear free-energy relationship and to develop five new linear free-energy relationships for predicting water-sc-CO2 partitioning coefficients. A total of four of the models targeted a single class of organic compounds. Unlike models that utilize Abraham solvation parameters, the new relationships use vapor pressure and aqueous solubility of the organic compound at 25 °C and CO2 density to predict partitioning coefficients over a range of temperature and pressure conditions. The compound class models provide better estimates of partitioning behavior for compounds in that class than does the model built for the entire data set.

Measurement of Setschenow constants for six hydrophobic compounds in simulated brines and use in predictive modeling for oil and gas systems.

Treatment and reuse of brines, produced from energy extraction activities, requires aqueous solubility data for organic compounds in saline solutions. The presence of salts decreases the aqueous solubility of organic compounds (i.e. salting-out effect) and can be modeled using the Setschenow Equation, the validity of which has not been assessed in high salt concentrations. In this study, we used solid-phase microextraction to determine Setschenow constants for selected organic compounds in aqueous solutions up to 2-5 M NaCl, 1.5-2 M CaCl2, and in Na-Ca binary electrolyte solutions to assess additivity of the constants. These compounds exhibited log-linear behavior up to these high NaCl concentrations. Log-linear decreases in solubility with increasing salt concentration were observed up to 1.5-2 M CaCl2 for all compounds, and added to a sparse database of CaCl2 Setschenow constants. Setschenow constants were additive in binary electrolyte mixtures. New models to predict CaCl2 and KCl Setschenow constants from NaCl Setschenow constants were developed, which successfully predicted the solubility of the compounds measured in this study. Overall, data show that the Setschenow Equation is valid for a wide range of salinity conditions typically found in energy-related technologies.

Partitioning behavior of organic contaminants in carbon storage environments: a critical review.

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.