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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. Reversible Cl ₂ /Cl ^– Redox for Low-Temperature Aqueous Batteries

   https://doi.org/10.1021/acsenergylett.2c02757  

   Sui, Yiming; Lei, Ming; Yu, Mingliang; Scida, Alexis; Sandstrom, Sean K.; Stickle, William; O’Larey, Timothy D.; Jiang, De-en; Ji, Xiulei (February 2023, ACS Energy Letters)
3. Spatially Resolved Product Speciation during Struvite Synthesis from Magnesite (MgCO ₃ ) Particles in Ammonium (NH ₄ ⁺ ) and Phosphate (PO ₄ ^3– ) Aqueous Solutions

   https://doi.org/10.1021/acs.jpcc.8b12252  

   Lu, Baoying; Kiani, Daniyal; Taifan, William; Barauskas, Dovydas; Honer, Kenneth; Zhang, Lihua; Baltrusaitis, Jonas (March 2019, The Journal of Physical Chemistry C)
4. The reaction of alkyl hydropersulfides (RSSH, R = CH ₃ and ^t Bu) with H ₂ S in the gas phase and in aqueous solution

   https://doi.org/10.1039/C8CP05503C  

   Zhang, Linxing; Zhang, Xinhao; Wu, Yun-Dong; Xie, Yaoming; Fukuto, Jon M.; Schaefer, Henry F. (January 2019, Physical Chemistry Chemical Physics)

   The RSSH + H 2 S → RSH + HSSH reaction has been suggested by numerous labs to be important in H 2 S-mediated biological processes. Seven different mechanisms for this reaction (R = CH 3 , as a model) have been studied using the DFT methods (M06-2X and ωB97X-D) with the Dunning aug-cc-pV(T+d)Z basis sets. The reaction of CH 3 SSH with gas phase H 2 S has a very high energy barrier (>45 kcal mol −1 ), consistent with the available experimental observations. A series of substitution reactions R 1 –S–S–H + − S–R 2 (R 1 = Me, t Bu, Ad, R 2 = H, S–Me, S– t Bu, S–Ad) have been studied. The regioselectivity is largely affected by the steric bulkiness of R 1 , but is much less sensitive to R 2 . Thus, when R 1 is Me, all − S–R 2 favorably attack the internal S atom, leading to R 1 –S–S–R 2 . While for R 1 = t Bu, Ad, all − S–R 2 significantly prefer to attack the external S atom to form − S–S–R 2 . These results are in good agreement with the experimental observations. 

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5. Experimental study of the proton-transfer reaction C + H ₂ ⁺ → CH ⁺ + H and its isotopic variant (D ₂ ⁺ )

   https://doi.org/10.1039/D0CP04810K  

   Hillenbrand, Pierre-Michel; Bowen, Kyle P.; Dayou, Fabrice; Miller, Kenneth A.; de Ruette, Nathalie; Urbain, Xavier; Savin, Daniel W. (December 2020, Physical Chemistry Chemical Physics)

   We report absolute integral cross section (ICS) measurements using a dual-source merged-fast-beams apparatus to study the titular reactions over the relative translational energy range of E r ∼ 0.01–10 eV. We used photodetachment of C − to produce a pure beam of atomic C in the ground electronic 3 P term, with statistically populated fine-structure levels. The H 2 + and D 2 + were formed in an electron impact ionization source, with well known vibrational and rotational distributions. The experimental work is complemented by a theoretical study of the CH 2 + electronic system in the reactant and product channels, which helps to clarify the possible reaction mechanisms underlying the ICS measurements. Our measurements provide evidence that the reactions are barrierless and exoergic. They also indicate the apparent absence of an intermolecular isotope effect, to within the total experimental uncertainties. Capture models, taking into account either the charge-induced dipole interaction potential or the combined charge-quadrupole and charge-induced dipole interaction potentials, produce reaction cross sections that lie a factor of ∼4 above the experimental results. Based on our theoretical study, we hypothesize that the reaction is most likely to proceed adiabatically through the 1 4 A′ and 1 4 A′′ states of CH 2 + via the reaction C( 3 P) + H 2 + ( 2 Σ+g) → CH + ( 3 Π) + H( 2 S). We also hypothesize that at low collision energies only H 2 + ( v ≤ 2) and D 2 + ( v ≤ 3) contribute to the titular reactions, due to the onset of dissociative charge transfer for higher vibrational v levels. Incorporating these assumptions into the capture models brings them into better agreement with the experimental results. Still, for energies ≲0.1 eV where capture models are most relevant, the modified charge-induced dipole model yields reaction cross sections with an incorrect energy dependence and lying ∼10% below the experimental results. The capture cross section obtained from the combined charge-quadrupole and charge-induced dipole model better matches the measured energy dependence but lies ∼30–50% above the experimental results. These findings provide important guidance for future quasiclassical trajectory and quantum mechanical treatments of this reaction. 

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