Adsorption behavior of long-chain perfluoroalkyl substances on hydrophobic surface: A combined molecular characterization and simulation study.

Hydrophobic interaction is a prevalent sorption mechanism of poly- and perfluoroalkyl substances (PFAS) in natural and engineered environments. In this study, we combined quartz crystal microbalance with dissipation (QCM-D), atomic force microscope (AFM) with force mapping, and molecular dynamics (MD) simulation to probe the molecular behavior of PFAS at the hydrophobic interface. On a CH3-terminated self-assembled monolayer (SAM), perfluorononanoic acid (PFNA) showed ∼2-fold higher adsorption than perfluorooctane sulfonate (PFOS) that has the same fluorocarbon tail length but a different head group. Kinetic modeling using the linearized Avrami model suggests that the PFNA/PFOS-surface interaction mechanisms can evolve over time. This is confirmed by AFM force-distance measurements, which shows that while the adsorbed PFNA/PFOS molecules mostly lay flat, a portion of them formed aggregates/hierarchical structures of 1-10 nm in size after lateral diffusion on surface. PFOS showed a higher affinity to aggregate than PFNA. Association with air nanobubbles is observed for PFOS but not PFNA. MD simulations further showed that PFNA has a greater tendency than PFOS to have its tail inserted into the hydrophobic SAM, which can enhance adsorption but limit lateral diffusion, consistent with the relative behavior of PFNA/PFOS in QCM and AFM experiments. This integrative QCM-AFM-MD study reveals that the interfacial behavior of PFAS molecules can be heterogeneous even on a relatively homogeneous surface.

Comparative Degradation Kinetics Study of Polyamide Thin Films in Aqueous Solutions of Chlorine and Peracetic Acid Using Quartz Crystal Microbalance.

Polyamide thin film composite membranes are widely used in water reclamation. Peracetic acid (PAA) is an emerging wastewater disinfectant with a potential for membrane cleaning and disinfection; however, its interaction with polyamide remains poorly understood. This study employs quartz crystal microbalance with dissipation (QCM-D) to determine the PAA-induced degradation kinetics of polyamide thin films, in comparison with the conventional disinfectant-free chlorine (HOCl). Polyamide films showed a sorption phase followed by a degradation phase when exposed to PAA (1000 mg L-1) and HOCl (100 mg L-1) solutions. While the sorption phase in HOCl experiments was short (1.4-3.5 min) and followed a Boltzmann-sigmoidal model, it spanned over 3-33 h in PAA experiments and displayed a two-stage behavior. The latter kinetics are attributed to sequential processes of the physical sorption of PAA in polyamide films followed by PAA-induced polyamide oxidation. In the degradation phase, the HOCl-exposed films followed a rapid, two-step exponential decay reaching an equilibrium mass of ∼50% of the initial (wet) mass after ∼5 h of exposure. In contrast, the PAA-exposed films followed a Boltzmann-sigmoidal decay, with ∼80% of the initial (wet) mass remaining intact after >10 h of exposure. Fast force maps generated using atomic force microscopy showed a progressive increase in the morphological heterogeneity of the polyamide films in HOCl solution due to pitting, cracking, bulging, and eventual delamination under both flow and no-flow conditions. In contrast, PAA only formed small pits on the polyamide film under flow; in a stagnant PAA solution, the film had no visible changes even after ∼148 h of exposure. This is the first comparative study on the chemical and morphological changes in polyamide films induced by PAA and HOCl. The much higher compatibility of polyamide with PAA than with chlorine supports the potential of PAA being used as a halogen-free membrane cleaning/disinfecting agent.

Aggregation Behavior of Inorganic 2D Nanomaterials Beyond Graphene: Insights from Molecular Modeling and Modified DLVO Theory.

We report the comparative aggregation behavior of three emerging inorganic 2D nanomaterials (NMs): MoS2, WS2, and h-BN in aquatic media. Their aqueous dispersions were subjected to aggregation under varying concentrations of monovalent (NaCl) and divalent (CaCl2) electrolytes. Moreover, Suwanee River Natural Organic Matter (SRNOM) has been used to analyze the effect of natural macromolecules on 2D NM aggregation. An increase in electrolyte concentration resulted in electrical double-layer compression of the negatively charged 2D NMs, thus displaying classical Derjaguin-Landau-Verwey-Overbeek (DLVO)-type interaction. The critical coagulation concentrations (CCC) have been estimated as 37, 60, and 19 mM NaCl and 3, 7.2, and 1.3 mM CaCl2 for MoS2, WS2, and h-BN, respectively. Theoretical predictions of CCC by modified DLVO theory have been found comparable to the experimental values when dimensionality of the materials is taken into account and a molecular modeling approach was used for calculating molecular level interaction energies between individual 2D NM nanosheets. Electrostatic repulsion has been found to govern colloidal stability of MoS2 and WS2 while the van der Waals attraction has been found to govern that of h-BN. SRNOM stabilizes the 2D NMs significantly possibly by electrosteric repulsion. The presence of SRNOM completely stabilized MoS2 and WS2 at both low and high ionic strengths. While h-BN still showed appreciable aggregation in the presence of SRNOM, the aggregation rates were decreased by 2.6- and 3.7-fold at low and high ionic strengths, respectively. Overall, h-BN nanosheets will have higher aggregation potential and thus limited mobility in the natural aquatic environment when compared to MoS2 and WS2. These results can also be used to mechanistically explain fate, transport, transformation, organismal uptake, and toxicity of inorganic 2D NMs in the natural ecosystems.