Design and optimization of an innovative lanthanum/chitosan bead for efficient phosphate removal and study of process performance and mechanisms.

Presence of excessive phosphorus in surface waters is the main cause for eutrophication. In this study, a lanthanum/chitosan (La/CS) bead was prepared so as to provide a cost-effective solution to the problem. The optimization of bead for the treatment was conducted, leading to the optimal condition: 30 wt% La/CS bead at a dosage of 30 g L-1 (wet weight). A higher phosphate removal around 90% was obtained in pH 4.0-10.0. Most of uptake occurred in the first 2 h and the equilibrium was reached in about 6 h. Coexisting ions of Cl-, [Formula: see text] , [Formula: see text] , and [Formula: see text] had negligible effects on the treatment, while the presence of F- reduced the uptake by 10.39%. The maximum adsorption capacity of 261.1 mg-PO4·g-1 (dried weight) at pH 5.0 was achieved, which is much better than many reported La-based adsorbents. The adsorbed phosphate can be effectively recovered with an alkaline solution. A multi-cycle regeneration-reuse study illustrated that the treated water still met the phosphorus discharge standard. The characterization results demonstrated the disappearance of La(OH)3 and La2(CO3)3 on the bead and the formation of NH3+ … P and La-P groups after the adsorption, indicating the significant roles of ion exchange and electrostatic attraction on the uptake. The excellent performance found in this study clearly indicates that the optimized La/CS bead is promising in the treatment of phosphate and perhaps its recovery for industrial use.

Leaching of organic matters and formation of disinfection by-product as a result of presence of microplastics in natural freshwaters.

Microplastics (MPs) are ubiquitous in the environment that may cause negative impacts on the aquatic organisms and human health. They exist in water and wastewater, which are from several sources, such as inappropriate disposal and littering. Therefore, it is important to evaluate the characteristics of MPs in different water types and oxidation processes and study dissolved organic carbon (DOC) leaching and chloroform formation. A commonly existing plastic matter, polyethylene (PE) was placed in different waters and gone through the Fenton-like reaction and the chlorination. The result showed that the PE leached nearly a similar amount of DOC (<1 mg L-1), which was regardless of the water types and under low-dosed irradiation/dark environment. The leached DOC caused the chloroform formation after the chlorination in the waters. During the Fenton-like reaction with the PE, a higher amount of leached DOC (∼3 mg L-1) was detected compared with that in the chlorination (∼0.8 mg L-1). The degree of DOC leaching from the PE caused by the oxidation processes was reflected by the degree of surface structural damage on the PE. However, the chlorination resulted in a higher chloroform formation from the PE (∼20 µg L-1) as the Fenton-like reaction degraded the chloroform. The higher the sodium hypochlorite concentration, the higher the chloroform concentration. When the chloroform existed in the water with the PE, adsorption of chloroform onto the PE was initially observed; however the rate of volatilization would be higher than the rate of adsorption eventually. This study offers useful information for the risk assessment of MPs in our fresh water and drinking water and possible mitigation strategies.

An optimized CaO2-functionalized alginate bead for simultaneous and efficient removal of phosphorous and harmful cyanobacteria.

Simultaneous removal of phosphorus (P) and algae is important to mitigate eutrophication, however, it is rather challenging in remediation of harmful algal blooms (HABs)-contaminated water. In this study, a wet alginate bead functionalized by CaO2 particle formed layer by layer was prepared with an in-situ method and optimized to remove phosphorous and inhibit algae growth. The stable H2O2 release with a concentration level of 0.06 mM was observed for a period of 26 d. The content of peroxy groups (-O-O-) in the optimal bead was 0.44 mmol·g-1 through permanganate-based titration study. For solution with an initial phosphorous concentration of 10 mg·L-1, the removal was around 97% in pH 3.0-10.0. XRD, SEM, and XPS studies and kinetic modelings showed that removal of phosphorus was mainly due to formation of insoluble Ca-P compounds in the bead. The CaO2-functionalized bead inhibited algae growth with an effect lasting over 170 d, which was much better than liquid H2O2 and Ca(OH)2 bead; the phosphorous removal with an efficiency of about 70% was simultaneously obtained. Furthermore, the bead demonstrated to be effective in removing algae in the realistic water from a reservoir. In summary, this study shows that the CaO2-functionalized material is promising for simultaneous removal of phosphorous and management of HABs.

Cost-effective phosphorus removal from aqueous solution by a chitosan/lanthanum hydrogel bead: Material development, characterization of uptake process and investigation of mechanisms.

Excessive phosphorus is one of the main reasons leading to eutrophication that causes severe ecosystem imbalance and negative human health impacts. In this study, several chitosan (CS)/lanthanum (La) hydrogel beads were first synthesized and tested for phosphorus removal. The stable cross-linked CS/La hydrogel bead prepared with the optimized conditions of 10 wt% La/CS and 1.5 mL of 5% glutaraldehyde demonstrated exceptional performance in the removal. It removed phosphate effectively from an aqueous solution in the pH range from 2 to 7. The complete phosphate uptake was achieved at contact time of 6 h under the completely mixing batch condition. The experimental maximum adsorption capacity of 107.7 mg g-1 was observed at solution pH 4. The phosphate adsorption was well described by the Freundlich isotherm and the intraparticle surface diffusion model. Furthermore, the adsorbent was effectively regenerated and reused in a five-cycle adsorption-desorption operation. The removal of phosphate can be attributed to electrostatic attraction and ion exchange. Moreover, the bead was capable of removing heavy metals: copper, zinc and lead. This adsorbent may be served as a cost-effective material for the treatment of phosphorus-contaminated water so as to minimize the occurrence of eutrophication.

Adsorption of organic and inorganic arsenic from aqueous solution: Optimization, characterization and performance of Fe-Mn-Zr ternary magnetic sorbent.

Arsenic is a highly toxic pollutant and exists in inorganic and organic forms in groundwater and industrial wastewater. It is of great importance to reduce the arsenic content to lower levels in the water (e.g., <10 ppb for drinking) in order to minimize risk to humans. In this study, a Fe-Mn-Zr ternary magnetic sorbent was fabricated via precipitation for removal of inorganic and organic arsenate. The synthesis of sorbent was optimized by Taguchi method, which leads to an adsorbent with higher adsorption capacity. The adsorption of As(V) was pH dependent; the optimal removal was achieved at pH 2 and 5 for inorganic and organic As(V), respectively. Contact time of 25 h was sufficient for complete adsorption of both inorganic and organic As(V). The adsorption isotherm study revealed that the adsorbent performed better in sequestration of inorganic As(V) than that of organic As(V); both adsorption followed the Langmuir isotherm with maximum adsorption capacities of 81.3 and 16.98 mg g-1 for inorganic and organic As(V), respectively. The existence of anions in the water had more profound effect on the adsorption of organic As(V) than the inorganic As(V). The co-existing silicate and phosphate ions caused significantly negative impacts on the adsorption of both As(V). Furthermore, the existence of humic acid caused the deterioration of inorganic As(V) removal but showed insignificant impact on the organic As(V) adsorption. The mechanism study demonstrated that ion exchange and complexation played key roles in arsenic removal. This study provides a promising magnetic adsorptive material for simultaneous removal of inorganic and organic As(V).

Incorporation of lanthanum particles to polyethersulfone ultrafiltration membrane for specific phosphorus uptake: Method comparison and performance assessment.

It is known that phosphorus is a major contributor to the occurrence of eutrophication. As such, it is of importance to remove it from water. Nanofiltration (NF) has low phosphorus selectivity and requires a relatively high pressure to achieve the separation, though it is capable of removing phosphorus. In this paper, we report our findings of method development on fabrication and application of a lanthanum (La)-incorporated polyethersulfone (PES)/sulfonated polyphenylenesulfone membrane for phosphorus treatment. The performances of membranes fabricated by the in situ and ex situ methods were examined in a series of batch adsorption and dead-end filtration experiments. The membrane fabricated by the in situ method demonstrated higher adsorption capacity (48.0 mg/g), faster kinetics (equilibrium in 6 h) and higher water permeance (>100 LMH/bar), which outperformed that by the ex situ method. Furthermore, the PES/La (in situ) membrane showed a comparable phosphate removal with a much higher permeance (about 20 times) than the NF90 (a nanofiltration commercial membrane). Moreover, the multiple cycles of filtration study showed that the membrane was reused satisfactorily in treating low-phosphate contaminated water and meeting the stringent phosphate standard limit of 0.15 mg/L. The removal of phosphate by the membranes was attributed to the mechanisms of ion exchange and electrostatic attraction/complexation. The study reported here provides a better approach in fabrication of functionalized membrane for water treatment, such as phosphate removal in either batch adsorption or membrane filtration process.

Microcystis aeruginosa removal by peroxides of hydrogen peroxide, peroxymonosulfate and peroxydisulfate without additional activators.

Harmful algal bloom (HAB) is one of the most globally severe challenges in ecological system and water safety. Hydrogen peroxide has been commonly used in the management/treatment. Solid oxidants (e.g., peroxymonosulfate (PMS) and peroxydisulfate (PDS)) may outperform liquid H2O2 due to ease in transportation, handling, and applications. However, the information on applications of PMS and PDS in algae treatment is limited. In this study, the two solid peroxides and H2O2 were investigated for the removal of the blue-green algae of Microcystis aeruginosa. H2O2 and PMS effectively removed algae in 2 d at pH 5.0, 7.0 and 9.0, while PDS was only effective at pH 5.0. The change in pH and the release of dissolved organic carbon were insignificant at 0.2 mM H2O2 and PMS. The PMS could degrade microcystin-LR and phycobiliproteins. The studies of phycobiliproteins degradation and scanning electron microscopy indicated that PMS might cause the cell inactivation mainly by damaging the chemical components in algae cell wall and membrane while H2O2 might mainly enter the cell to form oxidation pressure to kill algae. The scavenger experiments showed that radicals were not crucial in H2O2 and PDS applications. Similarly, the algae removal by PMS was obtained mainly by non-radical pathways; about 77% was direct PMS oxidation and no more than 3% was singlet oxygen-mediated process, while radical pathways of sulfate radical and hydroxyl radical accounted for 18% and 2%, respectively. For the realistic algae-contaminated natural water, the PMS effectively lasted for 60 d, while the H2O2 lasted for 12 d. This research work demonstrates that the PMS is promising in control of HAB. The findings can provide some useful design and application parameters of PMS technology for better management/treatment of algae-contaminated water.

Modification of polyvinylidene fluoride membrane by silver nanoparticles-graphene oxide hybrid nanosheet for effective membrane biofouling mitigation.

Membrane biofouling poses severe impacts on the membrane lifespan and performance. In this study, a silver nanoparticles-graphene oxide hybrid nanosheet (AgNPs-GO) was synthesized as a bactericidal agent for effective membrane biofouling mitigation. The surface polymerization between polyvinyl alcohol (PVA) and AgNPs-GO nanosheet improved the stability of inorganic biocidal materials on the membrane surface and had a significant effect on the permeability and rejection performance of membranes. The PVA/AgNPs-GO modified hydrophilic polyvinylidene fluoride (H-PVDF) membrane exhibited an excellent anti-microbial activity in both static contact and filtration modes; nearly 100% inactivation of Pseudomonas aeruginosa in solution and 91% reduction in the membrane surface adhesion were found. The composite membrane with good stability and anti-microbial ability may offer an alternative to alleviate membrane biofouling problem.

Great enhancement in phosphate uptake onto lanthanum carbonate grafted microfibrous composite under a low-voltage electrostatic field.

Removal of phosphorus from water via cost-effective measures becomes important for water industry mainly due to eutrophication in waterbody. In our lab, a novel lanthanum carbonate-microfibrous composite (LC-MC) with good performance was previously synthesized for the removal of phosphorus. In this study, we further improved our technology by applying the electrostatic field (direct current, DC) to the adsorption system. It was showed that the applied DC can greatly improve the adsorption of phosphate in particular the adsorption capacity. Better removal was seen in the pH range of 5-9 at a higher temperature. The maximum adsorption capacity of 47.57 mg-PO43- g-1 was achieved, which was 1.4 times of that operated in the absence of applied DC. The adsorption equilibrium was established at the contact time of 240 min; the adsorption history was well described by the intraparticle surface diffusion model. The negative effect from oxygen-containing anions on the phosphate uptake followed the decreasing sequence of: humic acid > carbonate > nitrate > sulfate; on the other hand, the halogen anions had almost no influence on it. Finally, the mechanism study by XPS, XRD, and IR demonstrated that the ligand exchange played an important role in the electro-assisted phosphate uptake process.

Improvement of Ultrafiltration for Treatment of Phosphorus-Containing Water by a Lanthanum-Modified Aminated Polyacrylonitrile Membrane.

Phosphorus contamination in fresh water has posed a great risk to aquatic ecosystems and human health due to extensive eutrophication. In this paper, we are reporting a lanthanum (La)-modified aminated polyacrylonitrile (PAN) adsorptive membrane for effective decontamination of phosphorus from the simulated water. The PAN membrane was first aminated to introduce the amine group as an active site for La and then followed by the in situ precipitation of La particles. The kinetics study showed that the rapid adsorption occurred within the initial 4 h with the equilibrium established at 8 h. The membrane worked well in the acidic pH region, with optimal pH 4 and 5 without and with the pH control, respectively. The maximum adsorption capacities were 50 and 44.64 mg/g at pH 5 and 7, respectively. The adsorption of phosphorus was not affected by the existence of commonly existing anions except fluorides in water. In the filtration study, it was observed that the removal of phosphorus remained the optimum, although the operating pressure was increased from 1 to 3 bar. The modified membrane was able to treat 0.32 L of a 10 mg/L phosphate solution to meet the maximum allowable limit of 0.15 mg/L for the trade effluent. The mechanism study revealed that the removal was primarily associated with the ion exchange between a phosphorus ion and a hydroxyl group from the La particles.

A new adsorbent of gadolinium-1,4-benzenedicarboxylate composite for better phosphorous removal in aqueous solutions.

Phosphorus in wastewater has caused the occurrence of eutrophication. In this study, we synthesized gadolinium -1,4-benzenedicarboxylate (GdBDC), a new gadolinium composite that has not been reported, for the removal of phosphorus. The GdBDC was prepared by gadolinium with the terephthalic acid as an organic linker. It was found that the GdBDC performed very well in pH 4-9. The adsorption isotherm and kinetics were well described by the Langmuir isotherm and the pseudo-second-order kinetic equation, respectively. Furthermore, the GdBDC showed a much faster adsorption rate than many reported adsorbents; the adsorption equilibrium was established in 40-80 min that was dependent upon initial concentration; the adsorption capacity was as high as 166.91 mg/g. The effect of ionic strength and presence of other anions was insignificant for the adsorption. The uptake of phosphorus by the GdBDC was due to ligand exchange between organic linker and phosphate anion. Through this study, GdBDC was a promising and potential adsorbent for treating phosphorus containing wastewater.