A fundamental model for calculating interfacial adsorption of complex ionic and nonionic PFAS mixtures in the presence of mixed salts.

Per- and polyfluoroalkyl substances (PFAS) are emerging contaminants that have been used extensively as firefighting agents and in a wide range of commercial applications around the world. As many of the most-common PFAS components are surfactants, they readily accumulate at interfaces, a process that can govern their environmental fate. There are thousands of PFAS compounds, and they have nearly always been used as mixtures, so it is common to find many different PFAS components present together in the environment. Furthermore, the interfacial behavior of ionic PFAS can be strongly influenced by the presence of salts, with adsorption dependent on both the composition and concentration of salts present. Any predictions of PFAS interfacial behavior made without considering both the mixed nature of PFAS present, as well as the composition of the salts present, have the potential to be off by orders of magnitude. To date, models capable of making predictions of PFAS interfacial adsorption when both mixed PFAS and mixed salts are present have not been presented. The work described here addresses this need by extending a mass-action model developed previously by the authors to allow predictions in cases where complex combinations of mixed PFAS and mixed salts are present. Predictions of PFAS interfacial affinity for a range of PFAS mixture conditions and ionic strengths are verified using experimentally-measured surface tension data. The new model provides physically-realistic prediction of interfacial adsorption of a wide range of PFAS mixtures over a wide range of salt concentrations and compositions. The model is capable of predicting interfacial adsorption of ionic/nonionic PFAS mixtures in the presence of salts, and can also make predictions when there is competitive adsorption between different PFAS components, a common case in PFAS source zones where high concentrations of multiple components are present and in foam fractionation reactors.

Calculating PFAS interfacial adsorption as a function of salt concentration using model parameters determined from chemical structure.

Per- and polyfluoroalkyl substances (PFAS) are widely-detected environmental contaminants known to concentrate at surfaces and interfaces. Many of the most commonly-detected PFAS function as ionic surfactants under environmental conditions. The interfacial behaviors of ionic surfactants, including PFAS, are strongly dependent on salt concentration and composition, with interfacial affinity potentially varying by orders of magnitude for the same compound under different conditions. The work described here presents a tool for predicting the salt-dependent adsorption of PFAS compounds based entirely on chemical structure, something of great value for predicting the real-world environmental behavior of many of the large numbers of PFAS compounds for which experimental data are not available. The approach combines two different previously-developed models, one a mass-action model designed to predict the effects of salts on interfacial adsorption of ionic PFAS (the UNSW-OU salt model), and the second a group-contribution model designed to predict interfacial adsorption of PFAS in the absence of salt based on chemical structure. The challenge of combining the two models comes from the fact that both are based on different isotherms. The salt model can produce sigmoidal isotherms under salt-limited conditions (an isotherm shape that is supported by experimental evidence), while the group-contribution model can generate Langmuir parameters from calculations based on chemical structure. Equations were derived to determine salt model isotherm parameters from Langmuir parameters (either from the group-contribution model or experimental sources) by matching surface tension curves in the vicinity of the concentration of highest second derivative. Refined group-contribution model parameters were determined based on data from an additional 40 surface tension curves to allow improved structure-based predictions for important classes of PFAS that were not sufficiently well-represented in the original model. The resulting equations provide a tool allowing quantitative predictions of PFAS behavior under realistic environmental conditions for compounds for which little or no experimental data are available.

Using sequential H2O2 addition to sustain 1,2-dichloroethane detoxification by a nanoscale zerovalent iron-induced Fenton's system at a natural pH.

1,2-dichloroethane (1,2-DCA) is a chlorinated hydrocarbon used for polyvinyl chloride plastic production. As such, 1,2-DCA is a common persistent contaminant in saturated zones. While nanoscale zerovalent iron (NZVI) is considered an effective reductant for removing a wide range of chlorinated hydrocarbons, 1,2-DCA is resistant to reduction by NZVI as well as by modified forms of NZVI (e.g., sulfidated-NZVI). Hydroxyl radicals produced in Fenton's reaction can effectively degrade 1,2-DCA, but Fenton's reaction requires the acidification of saturated zones to achieve a groundwater pH of 3 to facilitate the catalytic reaction. To overcome this problem, this study has developed a sequential treatment process using an NZVI-induced Fenton-like reaction that can effectively degrade 1,2-DCA at an initially neutral pH range. The experiments were conducted using a high 1,2-DCA concentration (2000 mg/L) to evaluate the feasibility of using the treatment process at source zones. The process degraded 99% of 1,2-DCA with a pseudo-first-order rate constant of 0.49 h-1. Unlike the single-stage treatment process, the sequential treatment can control the used H2O2 concentration in the system, thus sustaining the reaction and resulting in more efficient 1,2-DCA degradation. To mimic subsurface conditions, batch experiments were conducted to remove 1,2-DCA sorbed in contaminated soil. The results show that 99% removal of 1,2-DCA was obtained within 16 h. Additionally, this study suggests that the NZVI can be used for at least three consecutive 1,2-DCA degradation cycles while maintaining high removal efficiency.

Predicting the impact of salt mixtures on the air-water interfacial behavior of PFAS.

Salts are known to have strong impacts on environmental behavior of per- and polyfluoroalkyl substances (PFAS) including air-water interfacial adsorption. Multivalent salts impact interfacial adsorption to a greater extent than monovalent salts. Models to make a priori predictions of PFAS interfacial adsorption in the presence of multiple salts with different ionic charges are needed given the need to predict PFAS environmental fate. This study further develops a mass-action model to predict the interfacial behavior of PFAS as a function of both salt valency and concentration. The model is validated using surface tension data for a series of monovalent and divalent salt mixtures over a wide range of ionic strengths (i.e., from no added salt to 0.5 M) as well as comparison to data from literature. This model highlights the disproportionate impact of multivalent salts on interfacial adsorption and the practical utility of the model for predicting interfacial adsorption in the presence of multiple monovalent and multivalent inorganic salts. Results suggest that failure to account for divalent salt, even when concentrations are much smaller than monovalent salt, under most environmentally relevant aqueous phase conditions will result in significant underpredictions of PFAS interfacial adsorption. Simple examples of PFAS distribution in a range of salt conditions in the vadose zone and in aerated-water treatment reactors highlight the predictive utility of the model.

A new framework for modeling the effect of salt on interfacial adsorption of PFAS in environmental systems.

Per- and polyfluoroalkyl substances (PFAS) are surface active contaminants of great environmental concern, due to their widespread historical use and their environmental persistence. Salts are known to have a profound influence on the interfacial behaviors of all ionic surfactants, including some of the most commonly detected PFAS. This work describes a new mass-action model for predicting the interfacial behavior of surfactants as a function of salt concentration. The three-parameter model is fit to interfacial tension data over a range of salt concentrations, and is then able to predict interfacial adsorption isotherms for the entire range from no added salt, up to 0.5 M added salt. The phenomenological nature of the model means that it is likely to provide more robust predictions for new systems and conditions than some of the existing empirical approaches, and the minimal number of adjustable parameters ensures that unique calibrations are possible with limited data. The model is found to be consistent with experimental data, and is bracketed by experimental values at low PFAS concentrations. Of particular interest, the model predicts the existence of sigmoidal adsorption isotherms at low salt concentrations, a deviation from isotherms calculated the commonly-used Szyszkowski equation; the observation is supported by a maximum in measured interfacial adsorption coefficient calculated from low-concentration surface tension measurements. Because adsorption affinities can vary by orders of magnitude with changing salt concentration, the ability to predict the effects of salt on adsorption is of critical importance for quantitative prediction of PFAS behavior in the environment.

A group-contribution model for predicting the physicochemical behavior of PFAS components for understanding environmental fate.

The factors controlling per- and polyfluoroalkyl substances (PFAS) environmental fate remains the subject of considerable debate and study. As surfactants, PFAS readily partition to interfaces, a property that controls their transport and fate. A group contribution model is developed to predict the extent to which PFAS partitions to the air-water interface. Langmuir adsorption and Szyszkowski equation parameters were fitted to literature air-water surface tension data for a range of PFAS and conventional hydrocarbon surfactants. This approach enabled the prediction of the impact of the hydrophilic head group, and other molecular components, on PFAS interfacial partitioning in instances when PFAS data are unavailable but analogous hydrocarbon surfactant data are available. The model was extended to predict a range of parameters (i.e., solubility, critical micelle concentration (CMC), KD, Koc and Kow) that are used to predict PFAS environmental fate, including long-range PFAS transport and in multimedia models. Model predictions were consistent with laboratory and field derived parameters reported in the literature. Additionally, the proposed model can predict the impact of pH and speciation on the extent of PFAS interfacial partitioning, a potentially important feature for understanding the behaviors of some ionizable PFAS, such as fluorinated carboxylic acids. The proposed model provides a conceptually straightforward method to predict a wide range of environmental fate parameters for a wide range of PFAS. As such, the model is a powerful tool that can be used to determine parameters needed to predict PFAS environmental fate.

Developing a roadmap to determine per- and polyfluoroalkyl substances-microbial population interactions.

We collected over 40 groundwater samples from a per- and polyfluoroalkyl substances (PFAS) impacted legacy fire fighting training area in Canada to develop an in-depth assessment of the relationship between PFAS and in situ microbial communities. Results suggest differential transport of PFAS of differing chain-length and head group. There is also evidence of PFAS degradation, in particular 6:2 FTS degradation. Although PFAS constituents were not major drivers of microbial community structure, the relative abundance of over one hundred individual genera were significantly associated with PFAS chemistry. For example, lineages within the Oxalobacteraceae family had strong negative correlations with PFAS, whilst the Desulfococcus genus has strong positive correlations. Results also suggest a range of genera may have been stimulated at low to mid-range concentrations (e.g., Gordonia and Acidimicrobium), with some genera potentially inhibited at high PFAS concentrations. Any correlations identified need to be further investigated to determine the underlying reasons for observed associations as this is an open field site with the potential for many confounding factors. Positive correlations may ultimately provide important insights related to development of biodegradation technologies for PFAS impacted sites, while negative correlations further improve our understanding of the potential negative effects of PFAS on ecosystem health.