Magnetic field-assisted adsorption of phosphate on biochar loading amorphous Zr-Ce (carbonate) oxide composite.

For metal-based phosphate adsorbents, the dispersity and utilization of surface metal active sites are crucial factors in their adsorption performance and synthesis cost. In this study, a biochar material modified with amorphous Zr-Ce (carbonate) oxides (BZCCO-13) was synthesized for the phosphate uptake, and the adsorption process was enhanced by magnetic field. The beside-magnetic field was shown to have a better influence than under-magnetic field on adsorption, with maximum adsorption capacities (123.67 mg P/g) 1.14-fold greater than that without magnetic field. The beside-magnetic field could also accelerate the adsorption rate, and the time to reach 90% maximum adsorption capacity decreased by 83%. BZCCO-13 has a wide range of application pHs from 5.0 to 10.0, with great selectivity and reusability. The results of XPS and ELNES showed that the "magnetophoresis" of Ce3+ under the magnetic field was the main reason for the enhanced adsorption performance. In addition, increased surface roughness, pore size and oxygen vacancies, enhanced mass transfer by Lorentz force under a magnetic field, all beneficially influenced the adsorption process. The mechanism of phosphate adsorption by BZCCO-13 could be attributed to electrostatic attraction and CO32-dominated ligand exchange. This study not only provided an effective strategy for designing highly effective phosphate adsorbents, but also provides a new light on the application of rare earth metal-based adsorbent in magnetic field.

Synchronously construction of hierarchical porous channels and cationic surface charge on lanthanum-hydrogel for rapid phosphorus removal.

Phosphorus (P) removal from wastewater is critical for ecosystem operation and resource recovery. To facilitate the recycling of the used absorbents through balancing their adsorption and desorption performance on P, in this work, a novel porous magnetic La(OH)3-loaded MAPTAC/chitosan (CTS)/polyethyleneimine (PEI) ternary composite hydrogel (p-MTCH-La(OH)3) with enhanced bifunctional adsorption sites was synthesized by simultaneous dissolution of pre-embedded CaCO3 and CTS powder, followed by grafting PEI and loading La. Hierarchical porous channels promoted good dispersion of La(OH)3, bringing an excellent P adsorption capacity of 107.23 ± 4.96 mg P/g at neutral condition. PEI grafted with CTS increased the surface charge and enhanced the electrostatic attraction, which facilitated the desorption of P. The porous structure and abundant active sites also facilitated rapid adsorption with an adsorption rate constant of 0.1 g mg-1 h-1. p-MTCH-La(OH)3 maintained effective P adsorption despite co-existence with competing substances and after 5 cycles. Further mechanistic analysis indicated that La-P inner sphere complexation and LaPO4 crystalline transformation were the main pathways for P removal. However, electrostatic interactions contributed 17.5%-46.7% of the adsorption amount during the first 30 min of rapid adsorption, enabling 92.8% of the adsorbed P at this stage to be desorbed by alkaline solution. Based on the variations of adsorption and desorption capacity with adsorption time, a rapid unsaturated adsorption of 1-2 h was proposed to facilitate the recycling of the adsorbent. This study proposed a method to promote P adsorption and desorption by enhancing bifunctional adsorption sites, and proved that p-MTCH-La(OH)3 is a promising phosphate adsorbent.

Highly efficient P uptake by Fe3O4 loaded amorphous Zr-La (carbonate) oxides: Electrostatic attraction, inner-sphere complexation and oxygen vacancies acceleration effect.

Bimetallic oxides composites have received an increasing attention as promising adsorbents for aqueous phosphate (P) removal in recent years. In this study, a novel magnetic composite MZLCO was prepared by hybridizing amorphous Zr-La (carbonate) oxides (ZLCO) with nano-Fe3O4 through a one-pot solvothermal method for efficient phosphate adsorption. Our optimum sample of MZLCO-45 exhibited a high Langmuir maximum adsorption capacity of 96.16 mg P/g and performed well even at low phosphate concentration. The phosphate adsorption kinetics by MZLCO-45 fitted well with the pseudo-second-order model, and the adsorption capacity could reach 79% of the ultimate value within the first 60 min. The phosphate adsorption process was highly pH-dependent, and MZLCO-45 performed well over a wide pH range of 2.0-8.0. Moreover, MZLCO-45 showed a strong selectivity to phosphate in the presence of competing ions (Cl-, NO3-, SO42-, HCO3-, Ca2+, and Mg2+) and a good reusability using the eluent of NaOH/NaCl mixture, then 64% adsorption capacity remained after ten recycles. The initial 2.0 mg P/L in municipal wastewater and surface water could be efficiently reduced to below 0.1mg P/L by 0.07 g/L MZLCO-45, and the phosphate removal efficiencies were 95.7% and 96.21%, respectively. Phosphate adsorption mechanisms by MZLCO-45 could be attributed to electrostatic attraction and the inner-sphere complexation via ligand exchange forming Zr/La-O-P, -OH and CO32- groups on MZLCO-45 surface played important roles in the ligand exchange process. The existence of oxygen vacancies could accelerate the phosphate absorption rate of the MZLCO-45 composites.

Phosphate removal by a La(OH)3 loaded magnetic MAPTAC-based cationic hydrogel: Enhanced surface charge density and Donnan membrane effect.

Cationic hydrogels have received great attention to control eutrophication and recycle phosphate. In this study, a type of La(OH)3 loaded magnetic MAPTAC-based cationic hydrogel (La(OH)3@MMCH) was developed as a potential adsorbent for enhanced phosphate removal from aqueous environment. La(OH)3@MMCH exhibited high adsorption capacity of 105.72±5.99 mg P/g, and reached equilibrium within 2 hr. La(OH)3@MMCH could perform effectively in a wide pH range from 3.0 to 9.0 and in the presence of coexisting ions (including SO42-, Cl-, NO3-, HCO3-, SiO44- and HA). The adsorption-desorption experiment indicated that La(OH)3@MMCH could be easily regenerated by using NaOH-NaCl as the desorption agent, and 73.3% adsorption capacity remained after five cycles. Moreover, La(OH)3@MMCH was employed to treat surface water with phosphate concentration of 1.90  mg/L and showed great removal efficiency of 95.21%. Actually, MMCH showed high surface charge density of 34.38-59.38 meq/kg in the pH range from 3.0 to 11.0 and great swelling ratio of 3014.57% within 24 h, indicating that MMCH could produce the enhanced Donnan membrane effect to pre-permeate phosphate. Furthermore, the bifunctional structure of La(OH)3@MMCH enabled it to capture phosphate through electrostatic attraction and ligand exchange. All the results prove that La(OH)3@MMCH is a promising adsorbent for eutrophication control and phosphate recovery.

Nitrate removal from aqueous solutions by magnetic cationic hydrogel: Effect of electrostatic adsorption and mechanism.

Excessive nitrate (NO3-) is among the most problematic surface water and groundwater pollutants. In this study, a type of magnetic cationic hydrogel (MCH) is employed for NO3- adsorption and well characterized herein. Its adsorption capacity is considerably pH-dependent and achieves the optimal adsorption (maximum NO3--adsorption capacity is 95.88 ± 1.24 mg/g) when the pH level is 5.2-8.8. The fitting result using the homogeneous surface diffusion model indicates that the surface/film diffusion controls the adsorption rate, and NO3- approaches the center of MCH particles within 30 min. The diffusion coefficient (Ds) and external mass transfer coefficient (kF) in the liquid phase are 1.15 × 10-6 cm2/min and 4.5 × 10-6 cm/min, respectively. The MCH is employed to treat surface water that contains 10 mg/L of NO3-, and it is found that the optimal magnetic separation time is 1.6 min. The high-efficiency mass transfer and magnetic separation of MCH during the adsorption-regeneration process favors its application in surface water treatment. Furthermore, the study of the mechanism involved reveals that both -N+(CH3)3 groups and NO3- are convoluted in adsorption via electrostatic interactions. It is further found that ion exchange between NO3- and chlorine occurs.

Enhanced phosphate removal using zirconium hydroxide encapsulated in quaternized cellulose.

Zirconium-based materials are efficient adsorbent for aqueous phosphate removal. However, current zirconium-based materials still show unsatisfied performance on adsorption capacity and selectivity. Here, we demonstrate a zirconium hydroxide encapsulated in quaternized cellulose (QC-Zr) for the selective phosphate removal. Zirconium hydroxide nanoparticles were simultaneously generated in situ with the QC framework and firmly anchored in the three-dimensional (3D) cross-linked cellulose chains. The maximum P adsorption capacity of QC-Zr was 83.6 mg P/g. Furthermore, the QC-Zr shows high P adsorption performance in a wide pH range, generally due to the electrostatic effects of quaternized cellulose. The enhanced adsorption of P was also achieved in the presence of competing anions (including Cl-, NO3-, SO42-, SO44-) and humic acid (HA) even at a molar ratio up to 20 levels. The column adsorption capacity of QC-Zr reached 4000 bed volumes (BV) at EBCT = 0.5 min as the P concentration decreased from 2.5 to 0.5 mg/L. Mechanism study revealed that both -N+(CH3)3 groups and zirconium hydroxide were involved in phosphate adsorption via electrostatic interactions between -N+(CH3)3 and phosphate, and the formation of zirconium hydrogen phosphate (Zr(HPO4)x). The 31P nuclear magnetic resonance (NMR) study implied that P surface-precipitated and inner-sphere complexed with zirconium hydroxide at a ratio of 3:1.

Brilliant red X-3B uptake by a novel polycyclodextrin-modified magnetic cationic hydrogel: Performance, kinetics and mechanism.

A novel polycyclodextrin-modified magnetic cationic hydrogel (PCD-MCH) was developed and its performance, kinetics and mechanism for the removal of reactive brilliant red X-3B (X-3B) were studied. The results showed that the zeta-potential of PCD-MCH was 32.8 to 16.7mV at pH3.0-10.5. The maximum X-3B adsorption capacity of PCD-MCH was 2792.3mg/g. The adsorption kinetics could be well-described by the Weber-Morris model and the homogeneous surface diffusion model (HSDM). Diffusion stages corresponding to surface or film diffusion, intra-particle or wide mesopore diffusion, and narrow mesopore/micropore diffusion occurred at 0-120, 120-480 and 480-1200min, respectively. The latter two diffusion stages were rate-controlling for X-3B adsorption kinetics. At the initial X-3B concentration of 600mg/L, the diffusion coefficient (Ds) and external mass transfer coefficient in the liquid phase (kF) were 3×10-11cm2/min and 4.68×10-6cm/min, respectively. X-3B approaching the center of PCD-MCH particles could be observed at 360min. At the end of the third diffusion stage, the Cp at q/qe=0 was 45.20mg/L, which was close to the homogeneous Cp value of 46mg/L along the radius of PCD-MCH particles. At pH3.0-10.0, PCD-MCH showed stable X-3B adsorption capacities. After five regeneration-reuse cycles, the residual adsorption capacity of regenerated PCD-MCH was higher than 892.7mg/g. The corresponding adsorption mechanism was identified as involving electrostatic interactions, cyclodextrin cavities and hydrogen bonds, of which cyclodextrin cavities showed prominent capture performance towards dye molecules through the formation of inclusion complexes.

Optimizing slug bubble size for application of the ultra-thin flat sheet membranes in MBR: a comprehensive study combining CFD simulation and experiment.

Optimizing the slug bubble size specifically for ultra-thin flat sheet membranes in MBR systems can effectively enhance the scouring force and improve fouling control efficiency, thereby further advancing their targeted and widespread application. In this study, a three-dimensional model was developed based on the practical application to investigate the impact of slug bubbles on scouring performance in ultra-thin flat sheet MBR systems, encompassing their evolution, disturbance level, and shear stress. A membrane fouling probability index for quantifying the distribution of membrane fouling, along with a turbulence intensity index have been proposed. The findings revealed that the 20-mL slug bubble induced the highest disturbance level in the surrounding fluid, characterized by an instantaneous peak velocity of 0.63 m/s at the local system level, conducive to bubble scouring. And exerted the greatest shear stress effect, achieving the most effective reduction in membrane contamination, with a maximum shear stress of 1.82 Pa. The experimental validation conducted during the operational cycles confirmed that the scouring effect of 20-mL slug flow yielded in a maximum proportion of 48.16% within the low fouling probability region. The results provided evidence supporting the assertion that specific aeration conditions producing 20 mL of bubbles resulted in minimal membrane fouling, ensuring a more pronounced scouring effect. The combination anythsis of slug bubble characteristics and behaviors, integrating theoretical and experimental approaches, implied that 20 mL was the optimal bubble size in ultra-thin flat sheet MBR, which fulfilled the optimal air scouring effect.

Adsorption-electrochemical mediated precipitation for phosphorus recovery from sludge filter wastewater with a lanthanum-modified cellulose sponge filter.

In this study, the sludge filter wastewater is confirmed to investigate the effects of adsorption-electrochemical mediated precipitation (EMP) driven phosphorus recovery on the basis of lanthanum-modified cellulose sponge filter (LCLM) material. The adsorption-EMP method relies on in situ recovery phosphate (P) from the used desorption agent (NaOH-NaCl binary solution) via the formation of Ca5(PO4)3OH all while preserving the alkalinity of the desorption agents which benefited long-term application. The lanthanum content of LCLM was 9.0 mg/g, and the adsorption capacity reached 226.1 ± 15.2 mg P/g La at an equilibrium concentration of 3.9 mg P/L. After adsorption, 55.7 % of P was recovered, and the corresponding alkalinity increased from 1.9 mmol/L to 2.2 mmol/L. Adsorption mechanism analysis revealed that the high lanthanum usage of LCLM was attributed to the synergistic effect of the lattice oxygen of LaO and LaPO4·0.5H2O crystallite formation. Additionally, the Ca5(PO4)3OH was found precipitated in the precipitation in the cathode chamber (P-CC) rather than on the surface/section of cation exchange membrane (CEM) and cathode indicating that the P recovery process was controlled by the saturation of CaP species in the EMP system and the electromigration effect. These findings present a new strategy to promote the effective utilization of rare earth elements for P adsorption and demonstrate the potential application of adsorption-EMP systems in dephosphorization for wastewater treatment.

Identification of performance and cost in a new backwash method to clean the UF membrane: backwashing with low dosage of NaClO.

Ultrafiltration (UF) is widely used in wastewater reclamation treatments. Conventional backwashing is usually performed at regular time intervals (10-120 min) with permeate and without the addition of chemicals. Chemical enhanced backwashing (CEB) is usually applied after 70-90 filtration cycles with added chemicals. These cleaning methods cause membrane fouling and require costly chemicals. Instead of conventional backwashing, we propose herein a new backwashing method involving backwashing the effluent with low doses of sodium hypochlorite (NaClO) named as BELN. The performance and cost of UF backwashing were investigated with Beijing wastewater reclamation treatment. The results showed that the transmembrane pressure (TMP) increased from 33.2 to 48.2 kPa during hydraulic backwashing after 80 filtration cycles but increased from 33.3 to 39.3 kPa during backwashing with a low NaClO content of 20 mg/L. It was also noticed that the hydraulic-irreversible fouling index decreased from 5.58 × 10-3 m2/L to 3.58 × 10-3 m2/L with the new method. According to the three-dimensional fluorescence excitation-emission (3D-EEM), the response increased from 11.9 to 15.2% with BELN. Protein-like material was identified as the main component causing membrane fouling by blocking the membrane pores. The results indicated that the low dosage of NaClO effectively stripped the fouling layer. Finally, based on an economic evaluation, the capacity of the UF process was increased from 76,959 to 109,133 m3/d with the new method. The amount of NaClO consumed for Beijing wastewater reclamation treatment was similarly compared with the conventional backwashing in per year under BELN. The new method has good potential for application.

Electrical impedance spectroscopy as a potential tool to investigate the structure and size of aggregates during water and wastewater treatment.

Microscopic structure and size are important metrics for estimating aggregates environmental behaviors during water and wastewater treatment. However, in-situ determination of these characteristics is still a challenge. Here, we drew inspiration from a block disassembly process to propose an electrical impedance spectroscopy (EIS) method and constructed a generalized framework to associate macroscale electrical properties with microscopic structure and size-related characteristics of aggregates of different hierarchies. Extracted via EIS, the proposed models were verified to be capable of describing the self-similarity of aggregates and capturing the fractal and size information. Further, the proposed models exhibited a wide range of applications, which agrees well with the data gathered from various activated sludges, other colloids, and microgels in water and wastewater treatment. Finally, the EIS method was achieved online monitoring of fractal dimension and floc size during a sludge pre-oxidation conditioning process, which was elected as an example to illustrate the potential online applications of this EIS method in real water and wastewater environment. The obtained on-line data were used to indicate the potential suitable oxidation time during sludge pre-oxidation conditioning. These observations may inspire new methods of quantifying the aggregate structure and promote intelligent and dynamic decision-making during water and wastewater treatment.

Rapid and selective harvest of low-concentration phosphate by La(OH)3 loaded magnetic cationic hydrogel from aqueous solution: Surface migration of phosphate from -N+(CH3)3 to La(OH)3.

Phosphate is an important factor for the occurrence of surface water eutrophication, and is also a non-renewable resource which faces a potential depletion crisis. In this study, La(OH)3 loaded magnetic cationic hydrogel composite MCH-La(OH)3-EW was used to absorb low strength phosphate in simulated water and real water. The adsorption amount of MCH-La(OH)3-EW was 39.14 ± 0.31 mg P/g and the equilibrium time was 120 min at the initial phosphate concentration of 2.0 mg P/L. The adsorption process was a spontaneous endothermic reaction. MCH-La(OH)3-EW exhibited a high selectivity towards phosphate within pH of 4.0-10.0 or in the presence of co-existing ions (including Cl-, SO42-, NO3-, HCO3-, SiO32-) and humic acid. After 10 cycles of adsorption-desorption, the adsorption amount of regenerated MCH-La(OH)3-EW still remained at 63.4% of its maximum value. For the real water sample with phosphate concentration of 2.0 mg P/L, the phosphate removal efficiency could achieve 97.65-98.90% and the effluent turbidity was 2.10-4.27 NTU at the MCH-La(OH)3-EW dosage of 0.04 g/L. The adsorption mechanism analysis showed that both quaternary amine groups (-N+(CH3)3) and La(OH)3 of MCH-La(OH)3-EW were involved in the process of phosphate adsorption. The electrostatic interaction between phosphate and -N+(CH3)3 rapidly occurred at the initial stage of adsorption process, then the electrostatic absorbed phosphate migrated to La(OH)3 on the surface of MCH-La(OH)3-EW via ligand exchange to form inner-sphere complex. This phenomenon was conducive to phosphate adsorption kinetics by MCH-La(OH)3-EW.

La3+/La(OH)3 loaded magnetic cationic hydrogel composites for phosphate removal: Effect of lanthanum species and mechanistic study.

In this study, La3+(ion)/La(OH)3-W/La(OH)3-EW-loaded magnetic cationic hydrogel (MCH) composites were fabricated in situ and characterized to investigate the effects of lanthanum species on phosphate adsorption. The corresponding maximum P adsorption capacities of MCH-loaded La3+(ion) (MCH-La3+(ion)), La(OH)3-W (MCH-La(OH)3-W), and La(OH)3-EW (MCH-La(OH)3-EW) were 70.5 ± 2.67, 69.2 ± 3.5, and 90.2 ± 2.9 mg P/g, respectively. Furthermore, for MCH-La(OH)3-EW, the P adsorption capacity was maintained relatively stable and high at pH 4.5-11 because of the ligand exchange, electrostatic interactions, and Lewis acid-base interactions. The enhanced adsorption of P was achieved over a wide pH range, as well as in the presence of competing anions (including Cl-, NO3-, SO42-, HCO3- and SiO44-). Moreover, the exhausted MCH-La(OH)3-EW could be easily regenerated by a NaOH-NaCl desorption agent with above 72% adsorption capacity remained during five recycles. The column adsorption capacity of MCH-La(OH)3-EW reached ∼3500 bed volumes (BV) (∼67.7 mg P/g) as the concentration of P decreased from 5 mg/L to 0.1 mg/L. The ATR-IR, Raman, and XPS deconvolution results revealed that both MCH and lanthanum compounds, including La3+(ion), La(OH)3-W and La(OH)3-EW, contributed to the phosphate adsorption because of the electrostatic interactions between -N+(CH3)3 and phosphate, as well as the formation of LaPO4·xH2O.

Characterization and adsorption properties of a lanthanum-loaded magnetic cationic hydrogel composite for fluoride removal.

In this study, a novel lanthanum-loaded magnetic cationic hydrogel (MCH-La) was synthesized for fluoride adsorption from drinking water. The adsorption kinetics, isotherms, and effects of pH and co-existing anions on fluoride uptake by MCH-La were evaluated. FTIR, Raman and XPS were used to analyze the fluoride adsorption mechanism of MCH-La. Results showed that MCH-La had positive zeta potential values of 23.6-8.0 mV at pH 3.0-11.0, with the magnitude of saturation magnetization up to 10.3 emu/g. The fluoride adsorption kinetics by MCH-La fitted well with the fractal-like-pseudo-second-order model, and the adsorption capacity reached 93% of the ultimate adsorption capacity within the first 10 min. The maximum fluoride adsorption capacity for MCH-La was 136.78 mg F(-)/g at an equilibrium fluoride concentration of 29.3 mg/L and pH 7.0. Equilibrium adsorption data showed that the Sips model was more suitable than the Langmuir and Freundlich models. MCH-La still had more than 100 mg of F(-)/g adsorption capacity at a strongly alkaline solution (pH > 10). The adsorption process was highly pH-dependent, and the optimal adsorption was attained at pH 2.8-4.0, corresponding to ligand exchange, electrostatic interactions, and Lewis acid-base interactions. With the exception of both anions of HCO3(-) and SiO4(4-), Cl(-), NO3(-), and SO4(2-) did not evidently prevent fluoride removal by MCH-La at their real concentrations in natural groundwater. The fluoride adsorption capacity of the regenerated MCH-La approached 70% of the fresh MCH-La from the second to fifth recycles. FTIR and Raman spectra revealed that C-O and CO functional groups on MCH contributed to the fluoride adsorption, this finding was also confirmed by the XPS F 1s spectra. Deconvolution of C 1s spectra before and after fluoride adsorption indicated that the carboxyl, anhydride, and phenol groups of MCH were involved in the fluoride removal.