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1. Removal of Aqueous Uranyl and Arsenate Mixtures after Reaction with Limestone, PO ₄ ^3– , and Ca ²⁺

   https://doi.org/10.1021/acs.est.3c03809  

   Meza, Isabel; Hua, Han; Gagnon, Kaelin; Mulchandani, Anjali; Gonzalez-Estrella, Jorge; Burns, Peter C.; Ali, Abdul-Mehdi S.; Spilde, Michael; Peterson, Eric; Lichtner, Peter; et al (December 2023, Environmental Science & Technology)

   The co-occurrence of uranyl and arsenate in contaminated water caused by natural processes and mining is a concern for impacted communities, including in Native American lands in the U.S. Southwest. We investigated the simultaneous removal of aqueous uranyl and arsenate after the reaction with limestone and precipitated hydroxyapatite (HAp, Ca10(PO4)6(OH)2). In benchtop experiments with an initial pH of 3.0 and initial concentrations of 1 mM U and As, uranyl and arsenate coprecipitated in the presence of 1 g L−1 limestone. However, related experiments initiated under circumneutral pH conditions showed that uranyl and arsenate remained soluble. Upon addition of 1 mM PO43− and 3 mM Ca2+ in solution (initial concentration of 0.05 mM U and As) resulted in the rapid removal of over 97% of U via Ca−U−P precipitation. In experiments with 2 mM PO4 3− and 10 mM Ca2+ at pH rising from 7.0 to 11.0, aqueous concentrations of As decreased (between 30 and 98%) circa pH 9. HAp precipitation in solids was confirmed by powder X-ray diffraction and scanning electron microscopy/energy dispersive X-ray. Electron microprobe analysis indicated U was coprecipitated with Ca and P, while As was mainly immobilized through HAp adsorption. The results indicate that natural materials, such as HAp and limestone, can effectively remove uranyl and arsenate mixtures. 

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2. Synthesis and mechanistic investigations of pH-responsive cationic poly(aminoester)s

   https://doi.org/10.1039/c9sc05267d  

   Blake, Timothy R.; Ho, Wilson C.; Turlington, Christopher R.; Zang, Xiaoyu; Huttner, Melanie A.; Wender, Paul A.; Waymouth, Robert M. (March 2020, Chemical Science)

   null (Ed.)

   The synthesis and degradation mechanisms of a class of pH-sensitive, rapidly degrading cationic poly(α-aminoester)s are described. These reactive, cationic polymers are stable at low pH in water, but undergo a fast and selective degradation at higher pH to liberate neutral diketopiperazines. Related materials incorporating oligo(α-amino ester)s have been shown to be effective gene delivery agents, as the charge-altering degradative behavior facilitates the delivery and release of mRNA and other nucleic acids in vitro and in vivo . Herein, we report detailed studies of the structural and environmental factors that lead to these rapid and selective degradation processes in aqueous buffers. At neutral pH, poly(α-aminoester)s derived from N -hydroxyethylglycine degrade selectively by a mechanism involving sequential 1,5- and 1,6-O→N acyl shifts to generate bis( N -hydroxyethyl) diketopiperazine. A family of structurally related cationic poly(aminoester)s was generated to study the structural influences on the degradation mechanism, product distribution, and pH dependence of the rate of degradation. The kinetics and mechanism of the pH-induced degradations were investigated by 1 H NMR, model reactions, and kinetic simulations. These results indicate that polyesters bearing α-ammonium groups and appropriately positioned N -hydroxyethyl substituents are readily cleaved (by intramolecular attack) or hydrolyzed, representing dynamic “dual function” materials that are initially polycationic and transform with changing environment to neutral products. 

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3. Elementary reaction-based kinetic model for the fate of N -nitrosodimethylamine under UV oxidation

   https://doi.org/10.1039/D1EW00262G  

   Barrios, Benjamin; Kamath, Divya; Coscarelli, Erica; Minakata, Daisuke (August 2021, Environmental Science: Water Research & Technology)

   null (Ed.)

   UV photolysis is an effective process to remove nitrosamines from contaminated water resources. Nitrosamines represent a class of compounds with high potential for carcinogenicity and, therefore, there are serious concerns regarding their threat to human health and their environmental toxicity. Although the photochemical parameters of parent nitrosamines and their initial reaction pathways are well understood, the fate of nitrogen-containing species and reactive nitrogen species generated from nitrosamine degradation has not yet been elucidated. In this study, we develop an elementary reaction-based kinetic model for the photolysis of N -nitrosodimethylamine (NDMA) and the photochemical transformation products. We use density functional theory quantum mechanical calculations to calculate the aqueous-phase free energies of activation and reaction to investigate the kinetics and thermodynamics properties of the elementary reactions. We generate ordinary differential equations for all species involved in the identified reactions and solve them to obtain the time-dependent concentration profiles of NDMA and the degradation products at pH 3 and pH 7. The profiles are compared to experimental results in the literature to validate our elementary reaction-based kinetic model. This is the first study to develop an elementary reaction-based kinetic model for the photochemical reaction of NDMA and reactive nitrogen species. The findings of this study have a significant impact on the active research area of nitrosative stress and advanced oxidation processes that utilize nitrogen-containing compounds such as UV/nitrate and UV/chloramine advanced oxidation processes. 

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4. Pb Mineral Precipitation in Solutions of Sulfate, Carbonate and Phosphate: Measured and Modeled Pb Solubility and Pb2+ Activity

   https://doi.org/10.3390/min11060620  

   Li, Xinxin; Azimzadeh, Behrooz; Martinez, Carmen Enid; McBride, Murray B. (June 2021, Minerals)

   Lead (Pb) solubility is commonly limited by dissolution–precipitation reactions of secondary mineral phases in contaminated soils and water. In the research described here, Pb solubility and free Pb2+ ion activities were measured following the precipitation of Pb minerals from aqueous solutions containing sulfate or carbonate in a 1:5 mole ratio in the absence and presence of phosphate over the pH range 4.0–9.0. Using X-ray diffraction and Fourier-transform infrared spectroscopic analysis, we identified anglesite formed in sulfate-containing solutions at low pH. At higher pH, Pb carbonate and carbonate-sulfate minerals, hydrocerussite and leadhillite, were formed in preference to anglesite. Precipitates formed in the Pb-carbonate systems over the pH range of 6 to 9 were composed of cerussite and hydrocerussite, with the latter favored only at the highest pH investigated. The addition of phosphate into the Pb-sulfate and Pb-carbonate systems resulted in the precipitation of Pb3(PO4)2 and structurally related pyromorphite minerals and prevented Pb sulfate and carbonate mineral formation. Phosphate increased the efficiency of Pb removal from solution and decreased free Pb2+ ion activity, causing over 99.9% of Pb to be precipitated. Free Pb2+ ion activities measured using the ion-selective electrode revealed lower values than predicted from thermodynamic constants, indicating that the precipitated minerals may have lower KSP values than generally reported in thermodynamic databases. Conversely, dissolved Pb was frequently greater than predicted based on a speciation model using accepted thermodynamic constants for Pb ion-pair formation in solution. The tendency of the thermodynamic models to underestimate Pb solubility while overestimating free Pb2+ activity in these systems, at least in the higher pH range, indicates that soluble Pb ion-pair formation constants and KSP values need correction in the models. 

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5. Efficient Sequestration of Heavy Metal Cations by [Mo2S12]2− Intercalated Cobalt Aluminum-Layered Double Hydroxide

   https://doi.org/10.3390/inorganics13020050  

   Roy, Subrata Chandra; Donley, Carrie L; Islam, Saiful M (February 2025, Inorganics)

   Heavy metal cations such as Ag+, Pb2+, and Hg2+ can accumulate in living organisms, posing severe risks to biological systems, including humans. Therefore, removing heavy metal cations from wastewater is crucial before discharging them to the environment. However, trace levels and high-capacity removal of the heavy metals remain a critical challenge. This work demonstrates the synthesis and characterization of [Mo2S12]2− intercalated cobalt aluminum-layered double hydroxide, CoAl―Mo2S12―LDH (CoAl―Mo2S12), and its remarkable sorption properties for heavy metals. This material shows high efficiency for removing over 99.9% of Ag+, Cu2+, Hg2+, and Pb2+ from 10 ppm aqueous solutions with a distribution constant, Kd, as high as 107 mL/g. The selectivity order for removing these ions, determined from the mixed ion state experiment, was Pb2+ < Cu2+ ≪ Hg2+ < Ag+. This study also suggests that CoAl―Mo2S12 is not selective for Ni2+, Cd2+, and Zn2+ cations. CoAl―Mo2S12 is an efficient sorbent for Ag+, Cu2+, Hg2+, and Pb2+ ions at pH~12, with the removal performance of both Ag+ and Hg2+ cations retaining > 99.7% across the pH range of ~2 to 12. Our study also shows that the CoAl―Mo2S12 is a highly competent silver cation adsorbent exhibiting removal capacity (qm) as high as ~918 mg/g compared with the reported data. A detailed mechanistic analysis of the post-treated solid samples with Ag+, Hg2+, and Pb2+ reveals the formation of Ag2S, HgS, and PbMoO4, respectively, suggesting the precipitation reaction mechanism. 

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