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Our hypothesis that longer-chained perfluoroalkyl acids (PFAAs) outcompete shorter-chained PFAAs during adsorption was tested in this study, wherein the adsorption interactions of six frequently detected PFAAs with kaolinite clay were modeled and examined experimentally using various suspension compositions. Competitive adsorption of PFAAs on the kaolinite surface was observed for the first time, and longer-chained PFAAs outcompeted those with a shorter chain. The electrostatic repulsion between adsorbed PFAA molecules is a primary inhibitory factor in PFAA adsorption. An increase in aqueous sodium or hydrogen ion concentration weakened electrostatic repulsions and changed the adsorption free energy. Therefore, the adsorption of a shorter-chained PFAA with weaker hydrophobicity could occur at high sodium or hydrogen ion concentrations. The experimental and modeling data suggest that the adsorption of shorter-chained PFAAs (≤4 perfluorinated carbons) in freshwater with a typical ionic strength of 10(-2.5) is not thermodynamically favorable. Furthermore, by measuring the electrokinetic potential of kaolinite suspension in the presence of PFAAs, we found that the kaolinite surface became more negatively charged because of the adsorption of PFAAs. This observation indicates that the adsorbed PFAA molecules were within the electrical double layer of the kaolinite surface and that they contributed to the potential at the slipping plane. The possible alignments of adsorbed PFAA molecules on the kaolinite surface were then proposed.

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The most widely used approach for evaluating the performance of stormwater best management practices (BMPs) such as rain gardens is monitoring, but this approach can involve a long time period to observe a sufficient number and variety of storm events, a high level of effort, and unavoidable uncertainty. In this paper, we describe the development and evaluation of three approaches for performance assessment of rain gardens: visual inspection, infiltration rate testing, and synthetic drawdown testing. Twelve rain gardens in Minnesota underwent visual inspection, with four determined to be nonfunctional based on one or more of the following criteria: (1) presence of ponded water, (2) presence of hydric soils, (3) presence of emergent (wetland) vegetation, and (4) failing vegetation. It is believed that these rain gardens failed due to a lack of maintenance. For the remaining eight rain gardens, an infiltrometer was used to determine the saturated hydraulic conductivity (Ksat) of the soil surface at several locations throughout each basin in what is termed infiltration rate testing. The median Ksat values for the rain gardens ranged from 3 to 72 cm/h. Synthetic drawdown testing was performed on three rain gardens by filling the basins with water to capacity where possible and recording water level over time. The observed drain times for two of those rain gardens were in good agreement with predictions based on the median of the infiltrometer measurements. The observed drain time for the third rain garden was much greater than predicted due to the presence of a restrictive soil layer beneath the topsoil. The assessment approaches developed in this research should prove useful for determining whether the construction of the rain garden was performed properly, a rain garden is functioning properly, and for developing maintenance tasks and schedules.

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