Assessment of Ammoniacal Leaching Agents for Metal Cation Extraction from Construction Wastes in Mineral Carbonation.

The use of carbon mineralization to produce carbonates from alkaline industrial wastes is gaining traction as a method to decarbonize the built environment. One of the environmental concerns during this process is the use of acids, which are required to extract Ca2+ or Mg2+ from the alkaline waste to produce carbonates. Conventionally, acids such as hydrochloric, nitric, or sulfuric are used which allow for the highest material recovery but are corrosive and difficult to regenerate as they are utilized in a linear fashion and generate additional process waste. An alternative is to use regenerable protonatable salts of ammonia, such as ammonium chloride (AC) or ammonium sulfate, the former of which is used globally during the Solvay process as a reversible proton shuttle. In this study, we show that regenerable ammonium salts, such as AC (NH4Cl) and ammonium bisulfate (NH4HSO4), can be effectively used for material recovery and the production of calcium carbonate during the leaching of waste cement paste as an alternative to conventional acids such as HCl. Leaching kinetics, postreaction residue, and carbonate characterization were performed to assess the productivity of this system and potential uses of these materials downstream. The stabilization of vaterite was observed in the case of AC leaching, suggesting its importance in the kinetic stability of vaterite and suppression of calcite nucleation. Overall, this study motivates the use of alternative leaching agents, such as salts of ammonia, to facilitate material recovery and carbon capture from alkaline industrial wastes.

How chloride functions to enable proton conduction in photosynthetic water oxidation: Time-resolved kinetics of intermediates (S-states) in vivo and bromide substitution.

Chloride (Cl-) is essential for O2 evolution during photosynthetic water oxidation. Two chlorides near the water-oxidizing complex (WOC) in Photosystem II (PSII) structures from Thermosynechococcus elongatus (and T. vulcanus) have been postulated to transfer protons generated from water oxidation. We monitored four criteria: primary charge separation flash yield (P* â†’ P+QA-), rates of water oxidation steps (S-states), rate of proton evolution, and flash O2 yield oscillations by measuring chlorophyll variable fluorescence (P* quenching), pH-sensitive dye changes, and oximetry. Br-substitution slows and destabilizes cellular growth, resulting from lower light-saturated O2 evolution rate (-20 %) and proton release (-36 % ΔpH gradient). The latter implies less ATP production. In Br- cultures, protonogenic S-state transitions (S2 â†’ S3 â†’ S0') slow with increasing light intensity and during O2/water exchange (S0' â†’ S0 â†’ S1), while the non-protonogenic S1 â†’ S2 transition is kinetically unaffected. As flash rate increases in Cl- cultures, both rate and extent of acidification of the lumen increase, while charge recombination is suppressed relative to Br-. The Cl- advantage in rapid proton escape from the WOC to lumen is attributed to correlated ion-pair movement of H3O+Cl- in dry water channels vs. separated Br- and H+ ion movement through different regions (>200-fold difference in Bronsted acidities). By contrast, at low flash rates a previously unreported reversal occurs that favors Br- cultures for both proton evolution and less PSII charge recombination. In Br- cultures, slower proton transfer rate is attributed to stronger ion-pairing of Br- with AA residues lining the water channels. Both anions charge-neutralize protons and shepherd them to the lumen using dry aqueous channels.