Johns et al. fabricates and demonstrates the performance of functionalized polymer nanofibers for treatment of uranium in contaminated drinking water.

Urban stormwater runoff is a significant source of pollutants in surface water bodies. One such pollutant, 1H-benzotriazole, is a persistent, recalcitrant trace organic contaminant commonly used as a corrosion inhibitor in airplane deicing processes, automobile liquids, and engine coolants. This study explored the removal of 1H-benzotriazole from stormwater using bench-scale biofilter mesocosms planted with California native sedge, Carex praegracilis, over a series of three storm events and succeeding monitoring period. Benzotriazole metabolites glycosylated benzotriazole and benzotriazole alanine were detected and benzotriazole and glycosylated benzotriazole partitioning in the system were quantified. With a treatment length of seven days, 97.1% of benzotriazole was removed from stormwater effluent from vegetated biofilter mesocosms. Significant concentrations of benzotriazole and glycosylated benzotriazole were observed in the C. praegracilis leaf and root tissue. Additionally, a significant missing sink of benzotriazole developed in the vegetated biofilter mesocosms. This study suggests that vegetation may increase the operating lifespan of bioretention basins by enhancing the degradation of dissolved trace organic contaminants, thus increasing the sorption capacity of the geomedia.

Naturally occurring uranium is a widespread contaminant present in the water resources around the abandoned uranium mines in the southwest United States. A novel method for rapid uranium detection has been recently developed that relies on the sequestering of uranium by amidoximated polyacrylonitrile (AO-PAN) polymer mats and uses the Raman-active (ν1) symmetric stretch as the signal. The Raman signals obtained from uranium bearing AO-PAN were challenging to interpret due to an unknown uranyl speciation on the surface of the mats. Herein, we provide the synthesis and structural characterization of six model coordination compounds that contain acetamidoxime/benzamidoxime (AAO/BAO) coordinated to the uranyl cation: [UO2(η1-AAO)­(NO3)2(H2O)] (1), [UO2(η1-AAO)2(NO3)2] (2), [UO2(η2-BAO)2(CH3OH)2] (3), [(UO2)3(η2-BAO)3(μ2-NO3)3] (4), [(UO2)4(μ3-O)2(μ2-BAO)4(η1-BAO)4(H2O)2]­(NO3)4 (5), and [(UO2)4(μ3-O)2(μ2-BAO)4(η1-BAO)6Na­(NO3)2]­(NO3)3 (6). Solid-state Raman spectra of 1–6 showed dramatic differences in the uranyl ν1 symmetric stretch depending on the coordination of the amidoxime functional group. The assignments made from the solid-state Raman spectra were used to deconvolute the solution-state Raman spectra of uranyl–acetamidoxime/benzamidoxime methanol solutions at different metal to ligand molar ratios. At low molar ratios (1 U:1 AAO/BAO and 1 U:2 AAO/BAO) the dominant species is the uranyl coordinated via the η1-oxygen atom of the oxime group, while at high molar ratios (1 U:3 AAO/BAO and 1 U:4 AAO/BAO) the dominant species are a tetrameric uranyl−μ3-O-η1-amidoxime complex similar to compounds 5 and 6 and a uranyl−η2-amidoxime complex similar to compounds 3 and 4. Solid-state Raman spectra showed good agreement with Raman signals obtained from the uranyl–AO-PAN mats, demonstrating that binding motifs between uranyl and amidoxime in compounds 5 and 6 are the most representative of the uranyl species on the surface of the AO-PAN mats.

Polyaluminum cations, such as the MAl12 Keggin, undergo atomic substitutions at the heteroatom site (M), where nanoclusters with M = Al3+, Ga3+, and Ge4+ have been experimentally studied. The identity of the heteroatom M has been shown to influence the structural and electronic properties of the nanocluster and the kinetics of ligand exchange reactions. To date, only three ε-analogs have been identified, and there is a need for a predictive model to guide experiment to the discovery of new MAl12 species. Here, we present a density functional theory (DFT) and thermodynamics approach to predicting favorable heteroatom substitution reactions, alongside structural analyses on hypothetical ε-MAl12 nanocluster models. We delineate trends in energetics and geometry based on heteroatom cation properties, finding that Al3+–O bond lengths are related to heteroatom cation size, charge, and speciation. Our analyses also enable us to identify potentially isolable new ε-MAl12 species, such as FeAl127+. Based upon these results, we evaluated the Al3+/Zn2+/Cr3+ system and determined that substitution of Cr3+ is unfavorable in the heteroatom site but is preferred for Zn2+, in agreement with the experimental structures. Complimentary experimental studies resulted in the isolation of Cr3+-substituted δ-Keggin species where Cr3+ substitution occurs only in the octahedral positions. The isolated structures Na[AlO4Al9.6Cr2.4(OH)24(H2O)12](2,6-NDS)4(H2O)22 (δ-CrnAl13-n-1) and Na[AlO4Al9.5Cr2.5(OH)24(H2O)12](2,7-NDS)4(H2O)18.5 (δ-CrnAl13-n-2) are the first pieces of evidence of mixed Al3+/Cr3+ Keggin-type nanoclusters that prefer substitution at the octahedral sites. The δ-CrnAl13-n-2 structure also exhibits a unique placement of the bound Na+ cation, which may indicate that Cr3+ substitution can alter the surface reactivity of Keggin-type species.