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The development of an efficient adsorbent is required in tertiary wastewater treatment stages to reduce the phosphate–phosphorous content within regulatory levels (1 mg L−1 total phosphorous). In this study, a natural muscovite was used for the preparation of muscovite/zeolite composites and the incorporation of Fe3+/Mn2+ (oxy)hydroxide nanoparticles for the recovery of phosphate from synthetic wastewater. The raw muscovite MC and the obtained muscovite/sodalite composite LMC were used in the powder form for the phosphate adsorption in batch mode. A muscovite/analcime composite was obtained in the pellets PLMCT3 and monolith SLMCT2 forms for the evaluation in fixed-bed mode for continuous operation. The effect of pH, equilibrium and kinetic parameters on phosphate adsorption and its further reuse in sorption–desorption cycles were determined. The characterization of the adsorbents determined the Fe3+ and Mn2+ incorporation into the muscovite/zeolite composite's structure followed the occupancy of the extra-framework octahedral and in the framework tetrahedral sites, precipitation and inner sphere complexation. The adsorbents used in this study (MC, LMC, PLMCT3 and SLMCT2) were effective for the phosphate recovery without pH adjustment requirements for real treated wastewater. Physical (e.g., electrostatic attraction) and chemical (complexation reactions) adsorption occurred between the protonated Fe3+/Mn2+ (oxy)hydroxy groups and phosphate anions. Higher ratios of adsorption capacities were obtained by powder materials (MC and LMC) than the pellets and monoliths forms (PLMCT3 and SLMCT2). The equilibrium adsorption of phosphate was reached within 30 min for powder forms (MC and LMC) and 150 min for pellets and monoliths forms (PLMCT3 and SLMCT2); because the phosphate adsorption was governed by the diffusion through the internal pores. The adsorbents used in this study can be applied for phosphate recovery from wastewater treatment plants in batch or fixed-bed mode with limited reusability. However, they have the edge of environmentally friendly final disposal being promissory materials for soil amendment applications. [ABSTRACT FROM AUTHOR]

A parent Mg-Al-LDH was upgraded in its adsorption properties due to the incorporation of tri-metal species oxy(hydroxide) nanoparticles obtaining Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite for the phosphate recovery from simulated urban treated wastewater. The physicochemical properties of the synthesized Mn2+/Zn2+/Fe3+/Mg-Al-LDH make promising for real application without being environmentally harmful. The performance of Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was evaluated through batch adsorption assays. The support of iron, manganese, and zinc (oxy)hydroxide nanoparticles onto the parent Mg-Al-LDH structure was performed by precipitation, isomorphic substitution, and complexation reactions. The main improvement of the Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was the highest phosphate adsorption capacity (82.3 mg∙g−1) in comparison to the parent Mg-Al-LDH (65.3 mg∙g−1), in a broad range of concentrations and the effective phosphate adsorption at neutral pH (7.5) near to the real wastewater effluents conditions in comparison to the conventional limitations of other adsorbents. The effectiveness of Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was higher than the conventional metal LDHs materials synthesized in a single co-precipitation step. The phosphate adsorption onto Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite was described to be governed by both physical and chemical interactions. The support of Mn2+/Zn2+/Fe3+ oxy(hydroxide) nanoparticles over the parent Mg-Al-LDH was a determinant for the improvement of the phosphate adsorption that was governed by complexation, hydrogen bonding, precipitation, and anion exchange. The intra-particular diffusion also described well the phosphate adsorption onto the Mn2+/Zn2+/Fe3+/Mg-Al-LDH composite. Three specific stages of adsorption were determined during the phosphate immobilization with an initial fast rate, followed by the diffusion through the internal pores and the final equilibrium stage, reaching 80% of removal and the equilibrium within 1 h. The Mn2+/Zn2+/Fe3+/Mg-Al-LDH was strongly selective towards phosphate adsorption in presence of competing ions reducing the adsorption capacity at 20%. The Mn2+/Zn2+/Fe3+/Mg-Al-LDH has limited reusability, only 51% of the adsorbed phosphate could be recovered in the second cycle of the adsorption-desorption process. Around 14% of phosphate was loosely-bond to Mn2+/Zn2+/Fe3+/Mg-Al-LDH which brings the opportunity to be a new source of phosphorus. The use of eluted concentrates and the final disposal of the exhausted adsorbent for soil amendment applications can be an integral nutrient system (P, Mn, Zn, Fe) for agriculture purposes. [ABSTRACT FROM AUTHOR]

Hydrothermally synthesized Linde type A (LTA) and faujasite X (FAU-X) zeolites are low-cost and environmentally benign inorganic carriers for environmental applications. In this study, (oxy)hydroxides were incorporated onto LTA and FAU-X zeolites to promote the phosphate adsorption. The performance of LTA-Fe and FAU-X-Fe was evaluated through batch adsorption assays. A complete evaluation was performed to recover phosphate from synthetic wastewater. The effect of pH, concentration, equilibrium, and kinetic parameters on phosphate adsorption and its further reuse in sorption–desorption cycles were evaluated. LTA-Fe and FAU-X-Fe are effective for adsorption of phosphate at neutral (e.g., pH 7.0 ± 0.2) and in a broad range of phosphate concentrations. Higher ratios of adsorption capacities were obtained by synthetic zeolites enriched with iron in comparison to their parent forms. The phosphate adsorption occurred through hydrogen bonding and complexation reactions between protonated iron hydroxyl groups and phosphate anions. The phosphate monolayer adsorption was followed by diffusion through the internal pores and 80% of the equilibrium adsorption was reached within 50 min. The LTA-Fe and FAU-X-Fe can be used for phosphate recovery from wastewater treatment plants. The use of LTA-Fe and FAU-X-Fe in a tertiary wastewater treatment stage could allow to reduce the phosphate–phosphorous content, reaching the regulatory levels (equal 1 mg L−1 total phosphorous). The phosphate adsorption using LTA-Fe and FAU-X-Fe does not require pH adjustment, and it is endothermic. The reusability of both iron zeolites is limited, and they can be finally disposed for soil amendment applications. [ABSTRACT FROM AUTHOR]

The removal of nutrients (nitrogen (N), phosphorous (P)) from waste water has become a resource recovery option in recent regulations worldwide, as observed in the European Union. Although both of these nutrients could be recovered from the sludge line, > 70–75% of the N and P is discharged into the water line. Efforts to improve the nutrient recovery ratios have focused on developing low-cost technologies that use sorption processes. In this study, a natural zeolite (clinoptilolite type) in its potassium (K) form was impregnated with hydrated metal oxides and used to prepare natural hybrid reactive sorbents (HRS) for the simultaneous recovery of ammonium (NH 4 + ) and phosphate (PO 4 3 − ) from treated urban waste water. Three unfertile soils (e.g., one acidic and two basic) amended with N-P-K charged HRS were leached with deionized water (e.g. to simulate infiltration in the field) at two- and three-day time intervals over 15 different leaching cycles (equivalent to 15 bed volumes). The N-P-K leaching profiles for the three charged hybrid sorbents exhibited continuous nutrient release, with their values dependent on the composition of minerals in the soils. In the basic soil that is rich in illite and calcite, the release of potassium (K + ) and ammonium (NH 4 + ) is favoured by-ion exchange with calcium (Ca 2 + ) and accordingly diminishes the release of phosphate (PO 4 3 − ) due to its limited solubility in saturated calcite solutions (pH 8 to 9). The opposite is true for sandy soils that are rich in albite (both acidic and basic), whereas the release of NH 4 + and K + was limited and the values of both ions measured in the leaching solutions were below 1 mg/L. Their leaching solutions were poor in Ca 2 + , and the release of PO 4 3 − was higher (up to 12 mg P-PO 4 3 − /L). The nutrient releases necessary for plant growth were provided continuously and were controlled primarily by the soil mineral dissolution rates fixing the soil aqueous solution composition (e.g. pH and ionic composition; in particular, the presence of calcite is a determinant for nutrient release, especially in alkaline soils). The N-P-K charged HRS sorbents that were used for soil amendment may be an alternative for avoiding nutrient leaching and reaching the goals of soil sustainability in agriculture and reducing the nutrient overloading of surface waters. [ABSTRACT FROM AUTHOR]

The efficiency of wastewater treatment systems is measured in terms of physicochemical and biological parameters. In this study two-stages of treatment were evaluated for the phosphate and microbial removal from wastewater for agricultural purposes. Iron (oxy)hydroxide was incorporated into a natural clay for phosphate removal and essential oils (Eucalyptus globulus and Citrus limon) were used for microbial reduction from wastewater. An overall experimental evaluation was performed from synthetic wastewater and further validated in real wastewater in batch mode. Phosphate adsorption capacity of iron (oxy)hydroxide clay (PMFe 5) was three times higher than parent clay (PMFe 1). Phosphate removal by PMFe 5 was effective at neutral pH, which is attributed to physical and chemical adsorption mechanisms by means of hydrogen bonding adsorption and chemical complexation reactions, respectively. PMFe 5 removed phosphate and ammonium at 65.8% and 72.3%, respectively from real wastewater. On the other hand, the use of emulsions of Eucalyptus globulus and Citrus limon essential oils allowed the decrease of bacterial load from wastewater. The microbial reduction was more effective using Eucalyptus globulus than Citrus limon essential oil. The fecal and total coliforms were reduced to a maximum extent of 100% using Eucalyptus globulus at 100 mg L−1. Microbial content was reduced to 100% using Citrus limon at 1000 mg L−1. Thus, reusability of wastewater for irrigation purposes is possible using an iron clay and essential oils. The use of PMFe 5 as tertiary treatment stage could be crucial to recover phosphate–phosphorous from wastewater treatment plants reaching the regulatory levels. The content of total and fecal coliforms was also efficiently reduced using essential oils. On one hand, wastewater can be reused in irrigation activities according to the water quality standards. On the other hand, a nutrient enriched material can be provided as phosphate source for soil amendment application. The combination of both treatment technologies provides important agricultural supplies. [Display omitted] • An iron (oxy)hydroxide clay removed phosphate and ammonium from wastewater. • Essential oils were used for the reduction of total and fecal coliforms from wastewater. • Eucalyptus globulus essential oil at 100 mg L−1 reduced 100% of bacterial load. • Citrus limon essential oil 1000 mg L−1 reduced 100% of bacterial load. • Agricultural supplies obtained: nutrient-enriched clay and wastewater for irrigation. [ABSTRACT FROM AUTHOR]