Synthesis of amorphous-MnO2/Clinoptilolite and its utilization for NH4+-N oxidation in an anoxic environment.

Mediating the anoxic ammonia oxidation with manganese oxide (MnOx) can reduce the requirements of dissolved oxygen (DO) concentrations in constructed wetlands (CWs) and improve the removal of ammonium nitrogen (NH4+-N). Recent studies that employed natural manganese ore and/or mine waste as substrates in CWs may develop potentially negative environmental effects due to leachates. However, removing NH4+-N by anoxic ammonia oxidation is influenced by the crystal form of MnOx. In this study, a novel clinoptilolite-based amorphous-MnO2 (amorphous-MnO2/clinoptilolite) was synthesized by the sol-gel method as an alternative substrate to improve the efficiency of anoxic ammonia oxidation and reduce the impact of Mn ion leaching. According to the anoxic ammonia oxidation experiment of clinoptilolite, amorphous-MnO2/clinoptilolite, and manganese ore on NH4+-N, the amounts of NH4+-N removed were 24.55 mg/L/d, 44.55 mg/L/d, and 11.04 mg/L/d, respectively, and the initial NH4+-N concentration was 49.53 mg/L. These results indicated that the amorphous-MnO2/clinoptilolite had both the adsorption and the anoxic ammonia oxidation performance. The recycling experiment demonstrated that the effect of anoxic ammonia oxygen mediated by amorphous-MnO2 would not diminish with the gradual saturation of clinoptilolite for NH4+-N. Furthermore, the anoxic ammonia oxidation consumed NH4+-N in the clinoptilolite, which restored the adsorption capacity of the clinoptilolite and simultaneously decreased the leakage of manganese ions in the process, making it environmentally friendly. Therefore, the amorphous-MnO2/clinoptilolite provided an excellent substrate material for the constructed wetland under an anoxic environment, which greatly improved the nitrogen removal capacity compared to existing substrate materials.

Denitrification performance and characteristics of untreated corncob for enhanced nitrogen removal of municipal sewage with low C/N ratio.

Unpretreated corncob was applied in denitrification bio-filter (DNBF) and anoxic tank of AAO system, respectively, to treat sewage with low C/N ratio, and both two approaches achieved good denitrification performance. Although shorter HRT could effectively decrease effluent chroma and COD of corncob-DNBF, nitrogen removal efficiency declined unexpectedly. Higher internal reflux ratio was beneficial for corncob-AAO without damage to anoxic environment for denitrification, while there was no risk of effluent chroma and excessive COD. Different supplement modes could realize same denitrification effect with distinct advantages, which were higher specific denitrification rate and biomass amount, respectively. The latter mode, applying corncob at secondary treatment, was preferable for its operational stability and convenience. Stoichiometry analysis indicated the unit COD demand of AAO decreased from 5.70 to 5.04 g COD/g N after adding corncob, and the oxygen demand (or energy consumption of aeration) decreased as well. The dominant substrates decomposer in corncob-AAO altered to Kouleothrix (affiliated to phylum Chloroflexi), and the main denitrifying bacteria were unclassified_f__Methylophilaceae and Azospira. Accordingly, functional enzymes for degrading glucan, xylan and lignin and processing denitrification showed satisfying abundance in the integrated system, especially in the newly formed biofilm.

Enhancing ammonia oxidation mediated using different crystalline Mn-oxides in an anoxic environment.

A recent study found that the nitrogen cycle in marine sediments can occur under oxygen-limited conditions, and this is associated with a reduction of Mn (IV). However, the effect of MnO2 mediated anoxic ammonia oxidation in different sediments field test results are controversial. In this study, based on the fact that the crystal form and morphology of MnO2 in marine sediments are affected by geochemistry, α-, ß-, γ-MnO2 and amorphous MnO2 were prepared to explore the effect of the different MnO2 crystals on nitrogen removal under oxygen-limited conditions. The experimental results showed that the anoxic ammonia oxidation process was mediated by microorganisms, and the reaction was affected by pH and temperature. The optimal pH was 7 in the range of pH 4-9 and the optimal temperature was 25 °C in the range of 10 °C-40 °C. When the initial concentration of NH4+-N was 50 mg/L, the removal amounts of NH4+-N under an anoxic condition by α-, ß-, γ-MnO2 and amorphous MnO2 were 18.97 mg/L/d, 6.12 mg/L/d, 10.68 mg/L/d and 24.89 mg/L/d, respectively. During the anoxic oxidation between MnO2 and NH4+-N, the adsorption process occurred. In addition, the oxidation process produced both NOx--N (nitrification reaction) and gaseous nitrogen (ammonia oxidation reaction). The kinetic study showed that the NH4+-N removal process conformed to the pseudo-second-order rate model, and the removal rates were ranked as amorphous MnO2 > α- > Î³- > ß-MnO2. Together, these results showed that the amorphous MnO2 crystal structure was conducive to improve anoxic ammonia oxidation and nitrogen removal under oxygen-limited conditions.

Removal of V(V) From Solution Using a Silica-Supported Primary Amine Resin: Batch Studies, Experimental Analysis, and Mathematical Modeling.

Every year, a large quantity of vanadium-containing wastewater is discharged from industrial factories, resulting in severe environmental problems. In particular, V(V) is recognized as a potentially hazardous contaminant due to its high mobility and toxicity, and it has received considerable attention. In this study, a silica-supported primary amine resin (SiPAR) was prepared by in-situ polymerization, and the V(V) adsorption from the solution was examined. The as-prepared resin exhibited fast adsorption kinetics, and it could attain an equilibrium within 90 min for the V(V) solution concentration of 100 mg/L at an optimum pH of 4, whereas the commercial D302 resin required a treatment time of more than 3 h under the same conditions. Furthermore, the maximum adsorption capacity of the resin under optimum conditions for V(V) was calculated to be 70.57 mg/g. In addition, the kinetics and isotherm data were satisfactorily elucidated with the pseudo-second-order kinetics and Redlich-Peterson models, respectively. The silica-based resin exhibited an excellent selectivity for V(V), and the removal efficiency exceeded 97% in the presence of competitive anions at 100 mmol/L concentrations. The film mass-transfer coefficient (kf) and V(V) pore diffusivity (Dp) onto the resins were estimated by mathematical modeling. In summary, this study provided a potential adsorbent for the efficient removal of V(V) from wastewater.

Mn(VII) enhanced by CaSO3 to remove trace organic pollutants in high salt organic wastewater: Further enhancement of salinity.

The high concentration of salt in organic wastewater has a strong inhibitory effect on the removal of pollutants. A method for the efficient removal of trace pollutants in high-salinity organic wastewater was developed. This study investigated the effect of the combination of permanganate [Mn(VII)] and calcium sulfite [S(IV)] on pollutant removal in hypersaline wastewater. The Mn(VII)-CaSO3 system removed more pollutants from high-salinity organic wastewater than from normal-salinity wastewater. Chloride (increasing from 1 M to 5 M) and low concentration of sulfate (increasing from 0.05 M to 0.5 M) significantly enhanced the system's resistance to pollutants under neutral conditions. Despite the fact that Cl- can combine with the free radicals in the system and reduce their efficiency in removing pollutants, the presence of chloride ions greatly enhances the electron transfer rate in the system, promoting the conversion of Mn(VII) to Mn(III) and significantly increasing the reaction rate of Mn(III) as the primary active species. Therefore, chloride salts can greatly enhance the removal of organic pollutants by Mn(VII)-CaSO3. Although sulfate does not react with free radicals, a high concentration of sulfate (1 M) will affect the formation of Mn(III), which greatly weakens the removal effect of the entire system on pollutants. The system can still have a good pollutant removal effect with mixed salt. Altogether, this study demonstrates that the Mn(VII)-CaSO3 system offers new possibilities for the treatment of organic pollutants in hypersaline wastewater.

Glycine- and Alanine-Intercalated Layered Double Hydroxides as Highly Efficient Adsorbents for Phosphate with Kinetic Advantages.

Phosphate is the main cause of eutrophication. Layered double hydroxides (LDH) are considered to be promising phosphate adsorbents due to their high affinity and large capacity. In this study, we partially intercalated zwitterionic glycine and alanine into Cl-LDH (corresponding to MgAl-LDH with interlayer anion Cl-) and synthesized efficient inorganic-organic nanohybrids for phosphate removal with kinetic advantages. Gly-Cl-LDH, Ala-Cl-LDH and Cl-LDH were characterized, and their phosphate adsorption performances under the influence of environment factors (e.g., solution pH, coexisting anions, contact time and phosphate concentration) were investigated. The results show that Gly-Cl-LDH and Ala-Cl-LDH had larger specific surface areas and larger interlayer spaces than Cl-LDH, and exhibited better adsorption performance at a lower pH and better adsorption selectivity against SO42-. Kinetic experiments indicated that Gly-Cl-LDH and Ala-Cl-LDH can reduce phosphate concentrations to a lower level in a shorter time. The pseudo-second-order kinetic constants of Gly-Cl-LDH and Ala-Cl-LDH were 1.27 times and 3.17 times of Cl-LDH, respectively (R2 > 0.996). The maximum adsorption capacities derived from a Langmuir model of Cl-LDH, Gly-Cl-LDH and Ala-Cl-LDH are 63.2 mg-P/L, 55.8 mg-P/L and 58.2 mg-P/L, respectively, which showed superiority over the prevailing phosphate adsorbents. This research provides highly efficient adsorbents for removing phosphate from aqueous solutions.

Removal of micro organic pollutants in high salinity wastewater by comproportionation system of Fe(VI)/Fe(III): Enhancement of chloride and bicarbonate.

The high concentration of salt in industrial wastewater has a strong inhibitory effect on the removal of pollutants by free radicals. A method has been developed to effectively remove micro organic pollutants in industrial high-salinity wastewater. This study investigated the combination of ferrate(VI) (FeVIO42-, Fe(VI)) and Fe(III) on the reduction of the pollutants in synthetic high-salinity wastewater, while focusing on the effects of major inorganic substances. Whether in synthetic wastewater with or without salinity, Fe(VI)-Fe(III) process exhibited higher pollutants removal rates than Fe(VI). Both chloride (increasing from (2.2 ± 0.1) × 10-2 min-1 to (1.1 ± 0.03) × 10-1 min-1) and bicarbonate (increasing from (2.2 ± 0.1) × 10-2 min-1 to (1.1 ± 0.02) × 10-1 min-1) significantly enhanced the removal of pollutants by the Fe(VI)-Fe(III) process. Chloride changed the ionic strength of Fe(VI), but Fe(III) strengthened the formation of Fe(V)/Fe(IV) from FeO42-, which offset the effect of the decrease of HFeO4-. Bicarbonate complexed Fe(V)/Fe(IV), these complexes enhanced the oxidizing ability of Fe(V)/Fe(IV). Based on the Program Kintecus, Fe(IV) was proposed as the main iron species in Fe(VI)-Fe(III) system, and its concentration was 2 to 3 orders of magnitude higher than Fe(V) at pH 9.0. The enhancement of Fe(VI)-Fe(III) system was observed in the oxidation of pollutant in real wastewater. Overall, the Fe(VI)-Fe(III) process is a new option for treating organic pollutants in industrial high salinity wastewater.

Effects of iron-based substrate on coupling of nitrification, aerobic denitrification and Fe(II) autotrophic denitrification in tidal flow constructed wetlands.

The aerobic properties of nitrification and the anaerobic properties of denitrification in constructed wetlands are difficult to reconcile. In this study, two constructed wetlands were constructed with pyrite and steel slag in combination with zeolite, and their respective nitrification and denitrification capacities were evaluated under different tidal strategies. The steel slag wetland achieved 70.89 % and 46.04 % removal rates of NH4+-N and total nitrogen (TN), and the carbon consumption of denitrification was 1.51 mg BOD/mgN, which was better than pyrite wetland. Microbial analysis showed that Fe(II) autotrophic denitrification and aerobic denitrification occurred in both wetlands, and they were coupled with nitrification to achieve simultaneous removal of NH4+-N and TN. Microbial co-occurrence network and k-core decomposition analysis indicated that the core genus of steel slag wetlands was nitrifying bacteria. This study provides new insights into the application of tidal flow wetlands to treat rural sewage.