Synergistic effect on simultaneous treatment of Cr(VI) and chloramphenicol using a non-thermal plasma technology.

Toxic organic and heavy metal contaminants commonly exist in industrial waste stream(s) and treatment is of great challenge. In this study, a dielectric barrier discharge (DBD) non-thermal plasma technology was employed for the simultaneous treatment of two important contaminants, chloramphenicol (CAP) and Cr(VI) in an aqueous solution through redox transformations. More than 70% of CAP and 20% of TOC were degraded in 60 min, while Cr(VI) was completely removed in 10 min. The hydroxyl radicals were the main active species for the degradation. Meanwhile, the consumption of hydroxyl radicals was beneficial to the reduction of Cr(VI). The synergistic effect was investigated between CAP degradation and Cr(VI) reduction. The reduction of Cr(VI) would be enhanced in the presence of CAP with a low concentration and could be inhibited under a high concentration, because part of hydroxyl radicals could be consumed by the low-concentration CAP and the obtained intermediates with a higher kinetic rate. However, CAP with a high concentration could react with such reductive species as eaq- and •H, which could compete with Cr(VI) and inhibit the reduction. In addition, the presence of Cr(VI) enhanced the degradation and mineralization of CAP; the study of obtained intermediates indicated that the presence of Cr(VI) changed the degradation path of CAP as Cr(VI) would react with reductive species, enhance the generation of hydroxyl radicals, and cause more hydroxylation reactions. Moreover, the mechanism for the simultaneous redox transformations of CAP and Cr(VI) was illustrated. This study indicates that the DBD non-thermal plasma technology can be one of better solutions for simultaneous elimination of heavy metal and organic contaminants in aquatic environments.

Development and testing of alginate/C3N4porphyrin bead as a self-initiated Fenton photocatalyst for highly efficient atrazine removal.

Fenton reaction has been widely used for efficient treatment of organic wastewater. However, its applications are limited by such key factors as pH < 3. In this study, we developed, tested, and optimized an alginate/C3N4porphyrin bead (C3N4por-SA) as a recyclable photocatalyst in a photocatalysis-self-Fenton process to overcome these limitations. Porphyrin-modified C3N4 (C3N4por) was used as the H2O2 donator, while Fe(III) nodes served as the Fenton reagent. The as-prepared floating alginate/C3N4por bead utilized the light source as a driving force for the catalysis. Under visible light irradiation for 6 h, the model pollutant atrazine was degraded by 70.96 % by the optimized photocatalyst (named as C3N4por-SA-Fe1Ca5), demonstrating better photocatalytic performance than alginate/C3N4 beads. This improvement was attributed to the higher H2O2 yield from C3N4por. The alginate/C3N4por bead showed better photocatalytic activity even after several consecutive cycles and could easily be recovered for reuse. Furthermore, Fe(III)/Ca(II) bimetallic alginate bead exhibited better photocatalytic activity and a higher content of •OH radicals than the Ca(II) monometallic alginate beads, due to the ability of Fe(III) nodes to serve as a Fenton reagent. The influences of light sources, and commonly existing matters (namely SO42-, Cl-, CO32-, NO3-, and humic acid) were investigated. Moreover, the alginate/C3N4por bead demonstrated good photocatalytic performance in a simulated natural environment without the addition of extra H2O2, with an atrazine removal percentage of up to 96.3 % after 3-h irradiation. These findings indicated the great potential of alginate/C3N4por bead in practical applications.

Carbon capture and utilization by algae with high concentration CO2 or bicarbonate as carbon source.

Algae plays a key role in carbon capture and utilization (CCU) as it can capture and use the atmospheric CO2 for conversion of value-added products. Concentrated CO2 is common in flue gas and provides opportunities for algae cultivation. The drawbacks are mass transfer limitation, poor CO2 dissolution, and challenges to reach optimal levels for algal growth at given flue gas levels. Bicarbonate is flexible to be used as carbon source and owns the potential to enhance the efficiency of biological carbon fixation by algae. The requirements of algae strains are more stringent. To improve the industrial scale-up of CCU, system optimization is of great importance. More novel algal strains that can grow rapidly under harsh environment and provide valuable bio-products should be developed for large-scale production. Algae-driven CCU is promising for achieving carbon-neutrality.

Quantitative assessment of interactions of hydrophilic organic contaminants with microplastics in natural water environment.

The interaction between microplastics (MPs) and hydrophilic organic contaminants (HOCs) in natural water environment has recently raised great public attentions due to the potential toxicity to humans. However, the quantitative assessment is less studied. In this study, the interaction between ciprofloxacin (CIP) and ofloxacin (OFL) (two important HOCs) and virgin and aged polystyrene (PS) was investigated. The aged PS showed higher adsorption rate and capacity than the virgin PS, due to its larger surface area and more O-containing groups. The pH-dependent adsorption of CIP was higher than OFL on both virgin and aged PS; the maximum adsorption for both HOCs occurred at pH 5. The sequential orders of functional groups for the adsorption were discovered according to the study by the 2D correlation Fourier transform infrared spectroscopy. Several mechanisms existed for the interaction: (1) at 3.0 < pH < 5.0, the electrostatic attraction (EA) was inhibited while H-bond (HB) was dominant, accounting for > 60% of the total uptake; (2) at 5.0 < pH < 8.0, the contribution of EA increased to around 50-60% while HB decreased to 30-40%; (3) at 8.0 < pH < 10.0, EA, HB and π-π conjugation caused 30-40%, 25-40% and 20-45% of the total uptake, respectively; (4) at 10.0 < pH < 12.0, π-π conjugation accounted for 90-100%. Notably, higher adsorption of CIP was mainly attributed to the presence of secondary amino groups and its higher pKa value, correspondingly leading to the additional ordinary HB and negative charge-assisted HB, and EA interactions with PS. This study further provides clear evidences on the risk of MPs and HOCs on humans and aqueous living organisms.

Hierarchical hollow zeolite fiber in catalytic applications: A critical review.

Zeolites have widely been studied because of the better performance as catalysts and supports. However, the zeolites with only micropores have drawbacks in reactivity and selectivity due to limitation of diffusivity. The hollow zeolite fibers (HZF) with hierarchical porosity however can overcome the problem. The HZF can be synthesized by such methods as incorporated substrate removal method, solid-solid transformation method, co-axial electrospinning technology, dry-wet spinning technology, and hollow fiber incorporation method. The unique hierarchical porous structure leads to the great improvement in the diffusion efficiency of reactants. The catalytic zeolite membrane fibers are the most commonly used as they have stronger catalyst stability and higher catalytic selectivity. The HZFs are suitable in catalytic applications such as selective catalysis, CO preferential oxidation, air purification and wastewater treatment. In order that the HZFs can be applied to industrial operations, more research work should be carried out, such as developments of self-assembly pure HZFs, catalytic substrate incorporated HZFs, HZFs with gradient multicomponent zeolites and HZFs with nanoscale diameters.

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.

Gadolinium(III) terephthalate metal-organic framework for rapid sequestration of phosphate in 10 min: Material development and adsorption study.

Phosphorus with concentration above a few ppm in waters can easily cause eutrophication and poor water quality (e.g. algal blooming). In this study, we synthesized a non-porous gadolinium terephthalic acid (Gd-PTA) metal-organic framework (MOF) for efficient and rapid removal of phosphorus. Gd-PTA was prepared with gadolinium as the core metal center and terephthalic acid as the organic ligand, by which a well defined structure of new MOF was established. The adsorption isotherm and kinetics were well described by Langmuir isotherm equation and the intraparticle surface diffusion model, respectively. The maximum adsorption capacity was as high as 206.13- PO43- mg/g, which outperforms many reported and/or commercially available adsorbents (normmaly 5-150 PO43- mg/g). The adsorption was completed at the end of 10-min contact time, much faster than many reported adsorbents for uptake of anions (normmaly hours to days). The MOF performed very well in the uptake in phosphate containing solution with initial pH 3 to 9 and ionic strength (NaNO3) of 0-1 M, and in the presences of competiting sulphate, nitrate, carbonate and humic acid (each with 30, 50, and 100 mg/L). The absorption of phosphate was mainly controlled by ion exchange between phosphate and organic ligand of MOF as well as the interaction between unsaturated metal center of coordination and phosphate. This study demonstrates that the newly developed MOF reported here is a promising adsorbent for cost-effective treatment of phosphorus in water and wastewater.

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).

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.

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.

Simultaneous oxidation and removal of arsenite by Fe(III)/CaO2 Fenton-like technology.

Arsenite contaminated water is one of severe global environmental problems. It is challenging to treat As(III) pollution by a one-step technology. In this study, we developed a Fe(III)/CaO2 Fenton-like technology for the treatment of As(III). The simultaneous oxidation of arsenite and removal of arsenic were achieved with efficiencies of nearly 100% and 95.8% respectively, which outperforms conventional technologies. It worked well in pH 3 to 9, and in the presence of cationic heavy metals, anions and humic acid. Moreover, the PO43- inhibited the removal of As(III). •OH and 1O2 played the important roles in the oxidation of As(III). The Ca(II) derived from CaO2 made a significant contribution to the oxidation and removal of As(III). The SEM and XPS studies confirmed that the formation of Ca-Fe nascent colloid caused the effective removal of arsenic. Our study demonstrates that the one-step Fe(III)/CaO2 technology has a great potential for purification of the As(III)-contaminated water.

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.

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.

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.

An innovative lanthanum carbonate grafted microfibrous composite for phosphate adsorption in wastewater.

Excessive presence of phosphorus in waters can cause eutrophication, a global unsolved environmental problem that has caused harmful effects to our eco-system and the source of our drinking water. In the study presented in this paper, a novel lanthanum carbonate grafted microfibrous composite (LC-MC) adsorbent was synthesized aiming at removing large amount of phosphate in wastewater efficiently. An optimized LC-MC was firstly prepared. The most suitable pH for the phosphate uptake was pH 7 to 9. The adsorption showed similar behavior in a wide range of ionic strength. The presence of co-existing anions was proved to have a less significant effect on the removal. The adsorption isotherm data were better fitted by the Freundlich isotherm than the Langmuir isotherm. The equilibrium was reached at about 300 min of contact time. 80 % of original adsorption capacity can be achieved even after 5 cycles of adsorption- desorption operations, indicating great regenerative performance of the adsorbent. The adsorption mechanism study showed that the ligand exchange played a key role during the phosphate adsorption.

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.

Development and characterization of yttrium-ferric binary composite for treatment of highly concentrated arsenate wastewater.

Highly concentrated arsenic generated from industrial operation processes has posted a great thrust to humans. In this study, yttrium-ferric binary composite prepared through a simple co-precipitation method and applied for removing highly concentrated arsenic from the simulated arsenic-containing water. An optimal molar ratio of Y/Fe was determined as 8:1, which had a point of zero charge of around 7.0. The yttrium-ferric binary composite was aggregated by the nano-sized particles. The chemical state of yttrium and iron in the adsorbent was + III. The maximum adsorption capacities of the adsorbent towards arsenate (As(V)) were 401.8 mg-As/g at pH 4 and 288.7 mg-As/g at pH 7, respectively. A contact time of 8 h was sufficient to achieve 80% of the ultimate removal, faster than many reported/commercial water treatment materials. The existence of fluoride and phosphate ions significantly retarded the uptake of arsenic, indicating that likely the adsorbent was capable of adsorbing both contaminants. The mechanism study with several tools such as X-ray photoelectron spectroscopy (XPS) indicated that such functional groups as hydroxyl and carbonate groups participated in the As(V) adsorption process via ligand exchange followed by the inner-sphere complexation.