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Recalcitrant phosphorus (P) species, i.e., soluble non-reactive phosphorus (sNRP), are generally not effectively removed or recovered in conventional wastewater treatment processes. This was substantiated in our meta-analysis, which showed that nearly one-third of wastewater facilities’ effluent P was primarily in the non-reactive form. Transformation of sNRP to more readily removable/recoverable soluble reactive phosphorus (sRP) may offer a viable pathway to enhance P removal and recovery. Electrooxidation (EO) may offer one route for sNRP to sRP transformation. During EO, different sNRP transformation pathways may occur, influencing the extent and efficiency of sNRP transformations as a function of water quality. To explore these mechanisms, we conducted oxidant quenching tests as well as cyclic voltammetry and chronoamperometry experiments using a synthetic water matrix spiked with the sNRP compound beta-glycerol phosphate (BGP). We found that direct electron transfer was responsible for BGP transformation. To assess the applicability of EO for wastewater sNRP to sRP transformation and improved recoverability, EO was used to treat municipal wastewater centrate, followed by tests of sNRP recoverability using the P-selective LayneRT™ ion exchanger. Complete transformation of centrate sNRP to sRP was not achieved with EO, but subsequent removal of sNRP using ion exchange increased after 2 hr of EO treatment. Longer periods of EO treatment did not improve sNRP removal. Improved sNRP adsorption after EO was likely due to decreased competing organics in the centrate after EO treatment. Overall, this study showed that EO can improve sNRP removal using subsequent ion exchange and facilitate enhanced P recovery. 

Nitrogen gas (N2) fixation in the anode-respiring bacterium Geobacter sulfurreducens occurs through complex, multistep processes. Optimizing ammonium (NH4+) production from this bacterium in microbial electrochemical technologies (METs) requires an understanding of how those processes are regulated in response to electrical driving forces. In this study, we quantified gene expression levels (via RNA sequencing) of G. sulfurreducens growing on anodes fixed at two different potentials (−0.15 V and +0.15 V versus standard hydrogen electrode). The anode potential had a significant impact on the expression levels of N2 fixation genes. At −0.15 V, the expression of nitrogenase genes, such as nifH, nifD, and nifK, significantly increased relative to that at +0.15 V, as well as genes associated with NH4+ uptake and transformation, such as glutamine and glutamate synthetases. Metabolite analysis confirmed that both of these organic compounds were present in significantly higher intracellular concentrations at −0.15 V. N2 fixation rates (estimated using the acetylene reduction assay and normalized to total protein) were significantly larger at −0.15 V. Genes expressing flavin-based electron bifurcation complexes, such as electron-transferring flavoproteins (EtfAB) and the NADH-dependent ferredoxin:NADP reductase (NfnAB), were also significantly upregulated at −0.15 V, suggesting that these mechanisms may be involved in N2 fixation at that potential. Our results show that in energy-constrained situations (i.e., low anode potential), the cells increase per-cell respiration and N2 fixation rates. We hypothesize that at −0.15 V, they increase N2 fixation activity to help maintain redox homeostasis, and they leverage electron bifurcation as a strategy to optimize energy generation and use. 

Removing phosphorus (P) from water and wastewater is essential for preventing eutrophication and protecting environmental quality. Lanthanum [La(III)]-containing materials can effectively and selectively remove orthophosphate (PO4) from aqueous systems, but there remains a need to better understand the underlying mechanism of PO4 removal. Our objectives were to 1) identify the mechanism of PO4 removal by La-containing materials and 2) evaluate the ability of a new material, La2(CO3)3(s), to remove PO4 from different aqueous matrices, including municipal wastewater. We determined the dominant mechanism of PO4 removal by comparing geochemical simulations with equilibrium data from batch experiments and analyzing reaction products by X-ray diffraction and scanning transmission electron microscopy with energy dispersive spectroscopy. Geochemical simulations of aqueous systems containing PO4 and La-containing materials predicted that PO4 removal occurs via precipitation of poorly soluble LaPO4(s). Results from batch experiments agreed with those obtained from geochemical simulations, and mineralogical characterization of the reaction products were consistent with PO4 removal occurring primarily by precipitation of LaPO4(s). Between pH 1.5 and 12.9, La2(CO3)3(s) selectively removed PO4 over other anions from different aqueous matrices, including treated wastewater. However, the rate of PO4 removal decreased with increasing solution pH. In comparison to other solids, such as La(OH)3(s), La2(CO3)3(s) exhibits a relatively low solubility, particularly under slightly acidic conditions. Consequently, release of La3+ into the environment can be minimized when La2(CO3)3(s) is deployed for PO4 sequestration.