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1. Transition metal-doped MgO nanoparticles for nutrient recycling: an alternate Mg source for struvite synthesis from wastewater

   https://doi.org/10.1039/D0EN00660B  

   Silva, Manoj ; Murzin, Vadim ; Zhang, Lihua ; Baltrus, John ; Baltrusaitis, Jonas ( November 2020 , Environmental Science: Nano)

   null (Ed.)

   Nutrient nitrogen (N) and phosphorus (P) recovery from wastewater is an important challenge for enhanced environmental sustainability. Herein we report the synthesis and properties of mesoporous MgO nanoparticles doped with copper (Cu), iron (Fe), and zinc (Zn) as an alternative low-solubility high-abundance magnesium (Mg) source for crystalline struvite precipitation from nutrient-laden wastewater. Undoped MgO was shown to have the fastest phosphate (PO 4 3− ) adsorption kinetics with a k 2 value of 0.9 g g −1 min −1 at room temperature. The corresponding rate constant decreased for Cu–MgO (0.175 g g −1 min −1 ), Zn–MgO (0.145 g g −1 min −1 ), and Fe–MgO (0.02 g g −1 min −1 ). Undoped MgO resulted in the highest PO 4 3− removal at 94%, while Cu–MgO, Fe–MgO, and Zn–MgO resulted in 90%, 66% and 66%, respectively, under equivalent reaction conditions. All dopants resulted in the production of struvite as the main product with the incorporation of the transition metals into the struvite crystal lattice. X-ray absorption spectroscopy (XAS) showed that the majority of the Cu, Fe, and Zn were primarily in the +2, +3, and +2 oxidation states, respectively. XAS also showed that the Cu atoms exist in elongated octahedral coordination, while Fe was shown to be in octahedral coordination. Zn was shown to be in a complex disordered environment with octahedral sites coexisting with the majority of the tetrahedral sites. Finally, X-ray photoelectron spectroscopy data suggest a two-fold struvite surface enrichment with dopant metals, with Cu exhibiting an interesting new local binding structure. The dopant concentrations utilized were consistent with those found in natural Mg minerals, suggesting that (a) utilizing natural mineral periclase as the Mg source for struvite production can result in struvite formation, albeit at the expense of the reaction kinetics and overall yields, while also (b) supplying essential micronutrients, such as Zn and Cu, necessary for balanced nutrient uptake. 

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2. Toxicity of azoles towards the anaerobic ammonium oxidation (anammox) process

   https://doi.org/10.1002/jctb.6285  

   Lakhey, Nivrutti ; Li, Guangbin ; Sierra‐Alvarez, Reyes ; Field, Jim A. ( December 2019 , Journal of Chemical Technology & Biotechnology)

   Azoles are an important class of compounds that are widely used as corrosion inhibitors in aircraft de‐icing agents, cooling towers, semiconductor manufacturing and household dishwashing detergents. They also are important moieties in pharmaceutical drugs and fungicides. Azoles are widespread emerging contaminants occurring frequently in water bodies. Azole compounds can potentially cause inhibition towards key biological processes in natural ecosystems and wastewater treatment processes. Of particular concern is the inhibition of azoles to the nitrification process (aerobic oxidation of ammonium). This study investigated the acute toxicity of azole compounds towards the anaerobic ammonia oxidation (anammox) process, which is an important environmental biotechnology gaining traction for nutrient‐nitrogen removal during wastewater treatment. In this study, using batch bioassay techniques, the anammox toxicity of eight commonly occurring azole compounds was evaluated.

   The results show that 1H‐benzotriazole and 5‐methyl‐1H‐benzotriazole had the highest inhibitory effect on the anammox process, causing 50% decrease in anammox activity (IC₅₀) at concentrations of 19.6 and 17.8 mg L⁻¹, respectively. 1H‐imidazole caused less severe toxicity with an IC₅₀of 79.4 mg L⁻¹. The other azole compounds were either nontoxic (1H‐pyrazole, 1H‐1,2,4‐triazole and 1‐methyl‐pyrazole) or at best mildly toxic (1H‐benzotriazole‐5‐carboxylic acid and 3,5‐dimethyl‐1H‐pyrazole) towards the anammox bacteria at the concentrations tested.

   This study showed that most azole compounds tested displayed mild to low or no toxicity towards the anammox bacteria. The anammox bacteria were found to be far less sensitive to azoles compared to nitrifying bacteria. © 2019 Society of Chemical Industry

    

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3. Prospective Life Cycle Assessment and Cost Analysis of Novel Electrochemical Struvite Recovery in a U.S. Wastewater Treatment Plant

   https://doi.org/10.3390/su142013657  

   Morrissey, Karla G. ; English, Leah ; Thoma, Greg ; Popp, Jennie ( October 2022 , Sustainability)

   Nutrient recovery in domestic wastewater treatment has increasingly become an important area of study as the supply of non-renewable phosphorus decreases. Recent bench-scale trials indicate that co-generation of struvite and hydrogen using electrochemical methods may offer an alternative to existing recovery options utilized by municipal wastewater treatment facilities. However, implementation has yet to be explored at plant-scale. In the development of novel nutrient recovery processes, both economic and environmental assessments are necessary to guide research and their design. The aim of this study was to conduct a prospective life cycle assessment and cost analysis of a new electrochemical struvite recovery technology that utilizes a sacrificial magnesium anode to precipitate struvite and generate hydrogen gas. This technology was modeled using process simulation software GPS-X and CapdetWorks assuming its integration in a full-scale existing wastewater treatment plant with and without anaerobic digestion. Struvite recoveries of 18–33% were achieved when anaerobic digestion was included, with a break-even price of $6.03/kg struvite and $15.58/kg of hydrogen required to offset increased costs for recovery. Struvite recovery reduced aquatic eutrophication impacts as well as terrestrial acidification impacts. Tradeoffs between benefits from struvite and burdens from electrode manufacturing were found for several impact categories.

    

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4. Melamine-based functionalized graphene oxide and zirconium phosphate for high performance removal of mercury and lead ions from water

   https://doi.org/10.1039/d0ra07546a  

   Bakry, Ayyob M. ; Awad, Fathi S. ; Bobb, Julian A. ; Ibrahim, Amr A. ; El-Shall, M. Samy ( October 2020 , RSC Advances)

   null (Ed.)

   Heavy metal ions are highly toxic and widely spread as environmental pollutants. This work reports the development of two novel chelating adsorbents, based on the chemical modifications of graphene oxide and zirconium phosphate by functionalization with melamine-based chelating ligands for the effective and selective extraction of Hg( ii ) and Pb( ii ) from contaminated water sources. The first adsorbent melamine, thiourea-partially reduced graphene oxide (MT-PRGO) combines the heavier donor atom sulfur with the amine and triazine nitrogen's functional groups attached to the partially reduced GO nanosheets to effectively capture Hg( ii ) ions from water. The MT-PRGO adsorbent shows high efficiency for the extraction of Hg( ii ) with a capacity of 651 mg g −1 and very fast kinetics resulting in a 100% removal of Hg( ii ) from 500 ppb and 50 ppm concentrations in 15 second and 30 min, respectively. The second adsorbent, melamine zirconium phosphate (M-ZrP), is designed to combine the amine and triazine nitrogen's functional groups of melamine with the hydroxyl active sites of zirconium phosphate to effectively capture Pb( ii ) ions from water. The M-ZrP adsorbent shows exceptionally high adsorption affinity for Pb( ii ) with a capacity of 681 mg g −1 and 1000 mg g −1 using an adsorbent dose of 1 g L −1 and 2 g L −1 , respectively. The high adsorption capacity is also coupled with fast kinetics where the equilibrium time required for the 100% removal of Pb( ii ) from 1 ppm, 100 ppm and 1000 ppm concentrations is 40 seconds, 5 min and 30 min, respectively using an adsorbent dose of 1 g L −1 . In a mixture of six heavy metal ions at a concentration of 10 ppm, the removal efficiency is 100% for Pb( ii ), 99% for Hg( ii ), Cd( ii ) and Zn( ii ), 94% for Cu( ii ), and 90% for Ni( ii ) while at a higher concentration of 250 ppm the removal efficiency for Pb( ii ) is 95% compared to 23% for Hg( ii ) and less than 10% for the other ions. Because of the fast adsorption kinetics, high removal capacity, excellent regeneration, stability and reusability, the MT-PRGO and M-ZrP are proposed as top performing remediation adsorbents for the solid phase extraction of Hg( ii ) and Pb( ii ), respectively from contaminated water. 

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5. Estuarine Sediments Exhibit Dynamic and Variable Biogeochemical Responses to Hypoxia

   https://doi.org/10.1029/2018JG004663  

   Foster, S. Q. ; Fulweiler, R. W. ( April 2019 , Journal of Geophysical Research: Biogeosciences)

   Estuarine ecosystems are considered among the most valuable regions worldwide because of the wealth of ecosystem services they provide. Given their proximity to the land, they are also vulnerable to excessive nutrient inputs, which can lead to eutrophication and hypoxia. Water column hypoxia can dramatically alter sediment biogeochemistry, yet the response of specific processes varies widely. Predicting whether sediments are sources or sinks of ecologically and climatologically relevant nutrients and gases remains elusive, particularly for shallow coastal regions. In this study, we conducted experiments with sediments collected from Waquoit Bay (Massachusetts, United States) and measured dissolved nutrient and gas fluxes across the sediment‐water interface to investigate the impact of water column hypoxia (defined here as dissolved oxygen ≤3 mg/L) on three important ecosystem functions: nutrient regeneration, removal of reactive nitrogen, and the regulation of greenhouse gases. Under hypoxia we observed variable responses in sediment biogeochemical cycling, including little to no change in important nitrogen cycling processes such as ammonium efflux and nitrogen removal through denitrification. As expected, low oxygen conditions stimulated sediment phosphate efflux. This caused nutrient ratios for both nitrogen to phosphorus and silica to phosphorus in the overlying water to decrease by 50%. Such changes can alter both the composition of water column primary producers as well as the rate of primary production. Hypoxia led to an almost 60% decrease in sediment nitrous oxide consumption but had little impact on sediment methane emissions. Taken together, these experimental results suggest sediment biogeochemical cycling has variable and dynamic responses to hypoxia.

    

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