Electro-Enhanced Separation of Microsized Oil-in-Water Emulsions via Metallic Membranes: Performance and Mechanistic Insights.

Conventional separation membranes suffer from evitable fouling and flux decrease for water treatment applications. Herein, a novel protocol of electro-enhanced membrane separation is proposed for the efficient treatment of microsized emulsions (∼1 µm) by rationally designing robust electroresponsive copper metallic membranes, which could mitigate oil fouling and coenhance permeance (from ∼1026 to ∼2516 L·m-2·h-1·bar-1) and rejection (from ∼87 to ∼98%). High-flux Cu membranes exhibit superior ductility and electrical conductivity, enabling promising electroactivity. Separation performance and the fouling mechanism were studied under different electrical potentials and ionic strengths. Application of negative polarization into a large-pore (∼2.1 µm) Cu membrane is favorable to not only almost completely reject smaller-sized oil droplets (∼1 µm) but also achieve antifouling and anticorrosion functions. Moreover, surfactants around oil droplets might be redistributed due to electrostatic repulsion, which effectively enhances the steric hindrance effect between neighboring oil droplets, mitigating oil coalescence and consequently membrane fouling. Furthermore, due to the screening effect of surfactants, the presence of low-concentration salts increases the adsorption of surfactants at the oil-water interface, thus preventing oil coalescence via decreasing oil-water interfacial tension. However, under high ionic strengths, the fouling mechanism converts from cake filtration to a complete blocking model due to the reduced electrostatic repulsion between the Cu membrane and oil droplets. This work would provide mechanistic insights into electro-enhanced antifouling for not only oil emulsion separation but also more water treatment applications using rationally designed novel electroresponsive membranes.

Superhydrophobic Carbon Nanotube Network Membranes for Membrane Distillation: High-Throughput Performance and Transport Mechanism.

Despite increasing sustainable water purification, current desalination membranes still suffer from insufficient permeability and treatment efficiency, greatly hindering extensive practical applications. In this work, we provide a new membrane design protocol and molecule-level mechanistic understanding of vapor transport for the treatment of hypersaline waters via a membrane distillation process by rationally fabricating more robust metal-based carbon nanotube (CNT) network membranes, featuring a superhydrophobic superporous surface (80.0 ± 2.3% surface porosity). With highly permeable ductile metal hollow fibers as substrates, the construction of a superhydrophobic (water contact angle ∼170°) CNT network layer endows the membranes with not only almost perfect salt rejection (over 99.9%) but a promising water flux (43.6 L·m-2·h-1), which outperforms most existing inorganic distillation membranes. Both experimental and molecular dynamics simulation results indicate that such an enhanced water flux can be ascribed to an ultra-low liquid-solid contact interface (∼3.23%), allowing water vapor to rapidly transport across the membrane structure via a combined mechanism of Knudsen diffusion (more dominant) and viscous flow while efficiently repelling high-salinity feed via forming a Cassie-Baxter state. A more hydrophobic surface is more in favor of not only water desorption from the CNT outer surface but superfast and frictionless water vapor transport. By constructing a new superhydrophobic triple-phase interface, the conceptional design strategy proposed in this work can be expected to be extended to other membrane material systems as well as more water treatment applications.

Stable Zr-Based Metal-Organic Framework Nanoporous Membrane for Efficient Desalination of Hypersaline Water.

Treatment of hypersaline waters is a critical environmental challenge. Pervaporation (PV) desalination is a promising technique to address this challenge, but current PV membranes still suffer from challenging issues such as low flux and insufficient stability. Herein, we propose in situ nanoseeding followed by a secondary growth strategy to fabricate a high-quality stable metal-organic framework (MOF) thin membrane (UiO-66) for high-performance pervaporation desalination of hypersaline waters. To address the issue of membrane quality, a TiO2 nano-interlayer was introduced on coarse mullite substrates to favor the growth of a UiO-66 nanoseed layer, on which a well-intergrown UiO-66 selective membrane layer with thickness as low as 1 µm was finally produced via subsequent secondary growth. The PV separation performance for hypersaline waters was systematically investigated at different salt concentrations, feed temperatures, and long-term operation in different extreme chemical environments. Besides having nearly complete rejection (99.9%), the UiO-66 membrane exhibited high flux (37.4 L·m-2·h-1) for hypersaline waters, outperforming current existing zeolite and MOF membranes. The membrane also demonstrated superior long-term operational stability under various harsh environments (hypersaline, hot, and acidic/alkaline feed water) and mild fouling behavior. The rational design proposed in this study is not only applicable for the development of a high-quality UiO-66 membrane enabling harsh hypersaline water treatment but can also be potentially extended to other next-generation nanoporous MOF membranes for more environmental applications.

Exploring the optimal crop planting structure to balance water saving, food security and incomes under the spatiotemporal heterogeneity of the agricultural climate.

Crop planting provided foods, generated incomes, and consumed water resources to different extents under different spatiotemporal agroclimatic conditions. For balancing three aspects, targeting the rice, maize, wheat, and sorghum planted in Liaoning during the recent two decades, we established an integrated research framework consisting of water footprint (WF) accounting, clustering analysis, and fuzzy optimization programming to quantify the temporal trends and spatial distribution of water footprints, and optimized the planting structure under the different spatiotemporal agroclimatic conditions. Results showed that the maximum water footprint differences were 4166.73 m3/t and 4790.71 m3/t in spatial distribution and temporal series, respectively. Based on precipitation, we established 12 agroclimatic scenarios according to K-Means clustering. The fuzzy optimization result indicated that the planting area percent ranges of maize, wheat, rice, and sorghum in Liaoning province were 4.96%-98.62%, 0.00%-8.55%, 0.00%-18.18%, and 0.00%-95.04%, respectively under the different spatiotemporal conditions. This study's methods and results help make targeted decisions related to grain planting structure while considering the complex spatial-temporal conditions.

Cross-linked Graphene Oxide Framework Membranes with Robust Nano-Channels for Enhanced Sieving Ability.

It remains challenging for graphene oxide (GO) membranes to achieve highly efficient performance and sufficient stability for aqueous molecule/ion precise separations. Herein, a molecular-level rational structure design protocol was proposed to develop ceramic-based graphene oxide framework (GOF) membranes with significantly enhanced sieving performance and stability for efficient removal of salts and micropollutants. Via a molecular cross-linking strategy, interlayered nanochannels between GO nanosheets can be rationally designed, featuring precisely tailorable channel size, promising surface chemistries and remarkably robust stability suitable for aqueous separation. Due to a significantly decreased nanochannel size, cross-linking of TU (thiourea) molecule significantly improved monovalent salt rejection (95.6% for NaCl), outperforming existing state-of-the-art GO-based, commercial organic nanofiltration and emerging two-dimensional MoS2 membranes, while moderately decreasing water permeability. In comparison, the GOF membranes cross-linked with MPD (m-phenylenediamine) exhibited a simultaneous increase in permeability and rejection for both salts and micropollutants (21.0% and 53.3% enhancement for chloramphenicol (CAP) solution), breaking their conventional trade-off issue. Cross-linking mechanism indicates that more robust nanochannels were formed by stronger covalent bonds via dehydration condensation between amine (TU/MPD) and carboxyl groups (GO), and nucleophilic addition between amine (TU/MPD) and epoxy groups (GO). Molecule/ion separation mechanism involved size sieving (steric hindrance), electrostatic interaction, Donnan effect, and partial dehydration effect. This work provides a novel protocol for rationally designing size and surface chemistry of highly robust GO nanochannels at a subnanometer level to construct water-stable functional GOF membranes with enhanced sieving performance for water treatment applications.

Engineering a Nanocomposite Interlayer for a Novel Ceramic-Based Forward Osmosis Membrane with Enhanced Performance.

Rational design of a high-performance defect-free polyamide (PA) layer on a robust ceramic substrate is challenging for forward osmosis (FO) water treatment applications. In this study, we first demonstrated a robust ceramic-based thin-film composite (TFC) FO membrane by engineering a novel nanocomposite interlayer of titanium dioxide and carbon nanotube (TiO2/CNT). The structural morphologies and properties were systematically characterized for different substrates (without interlayer, with TiO2 interlayer, or with TiO2/CNT interlayer) and the corresponding ceramic-based TFC-FO membranes. Introduction of low roughness nanocomposite interlayers with decreased pore size created an interface with improved surface characteristics, favoring the formation of a defect-free nanovoid-containing PA layer with high cross-linking degree. The resulting ceramic-based FO membrane had a water permeability of approximately 2 L/(m2 h bar) and a NaCl rejection of 98%, showing simultaneous enhancements in both compared to the control membrane without an interlayer. Mechanism analysis indicates that such a special nanocomposite interlayer not only provided more active sites for the formation of a thinner defect-free nanovoid-containing PA layer without penetration into substrate but also acted as a highly porous three-dimensional network structure for rapid water transport. This work provides a novel protocol for rational design and fabrication of a high-performance multilayered inorganic FO membrane as well as extended applications in water treatment with enhanced performance.

Flexible Superhydrophobic Metal-Based Carbon Nanotube Membrane for Electrochemically Enhanced Water Treatment.

Treatment of highly saline wastewaters via conventional technology is a key challenging issue, which calls for efficient desalination membranes featuring high flux and rejection, low fouling, and excellent stability. Herein, we report a high-strength and flexible electro-conductive stainless steel-carbon nanotube (SS-CNT) membrane, exhibiting significantly enhanced anticorrosion and antifouling ability via a microelectrical field-coupling strategy during membrane distillation. The membrane substrates exhibited excellent mechanical strength (244.2 ± 9.8 MPa) and ductility, thereby overcoming the critical bottleneck of brittleness of traditional inorganic membranes. By employing a simple surface activation followed by self-catalyzed chemical vapor deposition, CNT was grown in situ on SS substrates via a tip-growth mechanism to finally form robust superhydrophobic SS-CNT membrane. To address the challenging issues of significant corrosion and fouling, using a negative polarization microelectrical field-coupling strategy, simultaneously enhanced antifouling and anticorrosion performance was realized for treatment of organic high salinity waters while exhibiting stable high flux and rejection via an electrostatic repulsion and electron supply mechanism. This application-oriented rational design protocol can be potentially used to extend toward high performance composite membranes derived from other electro-conductive metal substrates functionally decorated with CNT network and to other applications in water treatment.

A three-dimensional self-standing Mo2C/nitrogen-doped graphene aerogel: Enhancement hydrogen production from landfill leachate wastewater in MFCs-AEC coupled system.

A hydrothermal-annealing method was adopted to form nitrogen-doped graphene aerogel-supported molybdenum carbide (Mo2C/NGA) materials by using graphene oxide (GO), poly (propylene glycol) bis(2-aminopropyl ether) (D400 for short) and ammonium molybdate as precursors. The annealing temperature and GO/D400 wt ratio played an important role on the materials structure and electrocatalytic activity. When the annealing temperature reached to 800 °C, the Mo2C was formed as an active component and improved obviously the hydrogen evolution reaction (HER) activity. After introducing the appropriate amount of D400, the Mo2C/NGA material not only had a firm porous monolithic framework, but also presented an increasing HER activity. Further, the Mo2C/NGA-based microbial fuel cells-ammonia electrolysis cell (MFCs-AEC) coupled system was constructed and operated for higher hydrogen production. The coupled system produced hydrogen of 198 mL g-1Mo2C/NGA in simulated ammonia-rich wastewater. As using the actual landfill leachate wastewater as substrate, there was 79.2 mL g-1Mo2C/NGA of hydrogen production. All of these were attributed to the porous structure with an interconnected network and the nitrogen-doped structure of the NGA.

Stable Superhydrophobic Ceramic-Based Carbon Nanotube Composite Desalination Membranes.

Membrane distillation (MD) is a promising process for the treatment of highly saline wastewaters. The central component of MD is a stable porous hydrophobic membrane with a large liquid-vapor interface for efficient water vapor transport. A key challenge for current polymeric or hydrophobically modified inorganic membranes is insufficient operating stability, resulting in some issues such as wetting, fouling, flux, and rejection decline. This study presents an overall conceptual design and application strategy for a superhydrophobic ceramic-based carbon nanotube (CNT) desalination membrane having specially designed membrane structures with unprecedented operating stability and MD performance. Superporous and superhydrophobic surface structures with CNT networks are created after quantitative regulation of in situ grown CNT. The fully covered CNT layers (FC-CNT) exhibit significantly improved thermally and superhydrophobically stable properties under an accelerated stability test. Due to the distinctive structure of the superporous surface network, providing a large liquid-vapor superhydrophobic interface and interior finger-like macrovoids, the FC-CNT membrane exhibits a stable high flux with a 99.9% rejection of Na+, outperforming existing inorganic membranes. Under simple and nondestructive electrochemically assisted direct contact MD (e-DCMD), enhanced antifouling performance is observed. The design strategy is broadly applicable to be extended toward fabrication of high performance membranes derived from other ceramic or inorganic substrates and additional applications in wastewater and gas treatment.

Optimized anti-biofouling performance of bactericides/cellulose nanocrystals composites modified PVDF ultrafiltration membrane for micro-polluted source water purification.

The covalently functionalized cellulose nanocrystal (CNC) composites were synthesized by bonding common bactericides, such as dodecyl dimethyl benzyl ammonium chloride (DDBAC), ZnO and graphene oxide (GO) nanosheets, onto the CNC's surface. Then, the DDBAC/CNC, ZnO/CNC and GO/CNC nanocomposites modified polyvinylidene fluoride (PVDF) ultrafiltration membranes were fabricated by a simple one-step non-solvent induced phase separation (NIPS) process. The resultant hybrid membranes possessed porous and rough surfaces with more finger-like macropores that even extended through the entire cross-section. The hydrophilicity, permeability, antibacterial and antifouling performance and mechanism of the hybrid ultrafiltration membranes were evaluated and compared in detail, aiming at screening a superior hybrid membrane for practical application in micro-polluted source water purification. Among these newly-developed hybrid membranes, GO/CNC/PVDF exhibited an enhanced perm-selectivity with a water flux of 230 L/(m2 h bar) and humic acid rejection of 92%, the improved antibacterial activity (bacteriostasis rate of 93%) and antifouling performance (flux recovery rate (FRR) of >90%) being due to the optimized pore structure, higher surface roughness, incremental hydrophilicity and electronegativity. A lower biofouling level after three weeks' filtration of the actual micro-polluted source water further demonstrated that embedding the hydrophilic and antibacterial GO/CNC nanocomposite into the polymer matrix is an effective strategy to improve membrane anti-biofouling ability.

Fast start-up anammox process using Acyl-homoserine lactones (AHLs) containing supernatant.

N-dodecanoyl homoserine lactone (C12-HSL) was detected in the supernatant of an anammox granular sludge reactor (AGSR). C12-HSL could enhance the specific anammox activity of anammox biomass. Adding C12-HSL-containing AGSR supernatant into the continuously stirred tank reactors reduced the start-up time of the anammox process from 80 to 66days. Moreover, the nitrogen loading rate was also enhanced to 1.6 times that of the control reactor. AHLs could increase the secretion of extracellular polymeric substances and anammox obtained better enrichment with the addition of AHLs-containing AGSR supernatant. Denaturing gradient gel electrophoresis analysis further revealed that AHLs played a role in mediating microbial community parameters. In conclusion, adding AHL-containing supernatant could be an effective and economical way to accelerate the start-up of anammox.

Potential coupling effects of ammonia-oxidizing and anaerobic ammonium-oxidizing bacteria on completely autotrophic nitrogen removal over nitrite biofilm formation induced by the second messenger cyclic diguanylate.

The objective of this study was to investigate the influence of extracellular polymeric substance (EPS) on the coupling effects between ammonia-oxidizing bacteria (AOB) and anaerobic ammonium-oxidizing (anammox) bacteria for the completely autotrophic nitrogen removal over nitrite (CANON) biofilm formation in a moving bed biofilm reactor (MBBR). Analysis of the quantity of EPS and cyclic diguanylate (c-di-GMP) confirmed that the contents of polysaccharides and c-di-GMP were correlated in the AOB sludge, anammox sludge, and CANON biofilm. The anammox sludge secreted more EPS (especially polysaccharides) than AOB with a markedly higher c-di-GMP content, which could be used by the bacteria to regulate the synthesis of exopolysaccharides that are ultimately used as a fixation matrix, for the adhesion of biomass. Indeed, increased intracellular c-di-GMP concentrations in the anammox sludge enhanced the regulation of polysaccharides to promote the adhesion of AOB and formation of the CANON biofilm. Overall, the results of this study provide new comprehensive information regarding the coupling effects of AOB and anammox bacteria for the nitrogen removal process.

A bio-electrochemical membrane system for more sustainable wastewater treatment with MnO2/PANI modified stainless steel cathode and photosynthetic provision of dissolved oxygen by algae.

A competitive sewage treatment technology should meet the standard of water quality requirement and accomplish recovery of potential energy. This study presents such a new system, with coupled membrane bioreactor-microbial fuel cell features, which can not only treat wastewater, but also recovers energy from wastewater by electricity generation, and form a new resource by photosynthesis while providing the dissolved oxygen by algae. Specifically, in the system, the MnO2/polyaniline is used to modify the stainless steel mesh and to function well as system membrane and cathode, with satisfactory filtration and catalysis performance. The system enables continuous wastewater treatment with stable pollutant removal and electricity generation. Under the membrane flux of 119.4 Lm-2 h-1, a maximum power density of 1.2 W m-3 can be achieved, the algae multiply 6.1 times, and satisfactory wastewater treatment effect is achieved.

Effects of Inhibiting Acylated Homoserine Lactones (AHLs) on Anammox Activity and Stability of Granules'.

In this study, the effects of AHL-based QS signals on anammox activity and stability of granules' were investigated. Results clearly showed that the vanillin and porcine kidney acylase I could reduce the AHLs in anammox bacteria. Inactivation of AHLs by vanillin and porcine kidney acylase I depressed the nitrogen removal ability of anammox bacteria. A significant inhibition of specific anammox activity was observed when the concentration of vanillin and porcine kidney acylase I increased to 1 g/L. Anammox activity was depressed on enzyme level. Moreover, degradation of AHLs under vanillin and AHL-acylase exposure could result in anammox granules' disintegration. Further research showed that the contents of protein (PN) and polysaccharides (PS) in extracellular polymeric substances were reduced with AHLs blocked, and it further explained the instability and weakening strength of the anammox granules. The results of our investigation provided new insight into the AHL-based QS-regulated anammox activity, leading a potential way to enhance stability of anammox granules.

Polyaniline/reduced graphene oxide/Fe3O4 nano-composite for aqueous Hg(II) removal.

To ease the adsorbent recovery and to increase the adsorption capacity of polyaniline (PANI), aniline was polymerized in the presence of a solvothermally prepared nano-composite of reduced graphene oxide and Fe3O4 (RGO/Fe3O4). The polyaniline was formed along the RGO/Fe3O4 composite in transmission electron microscope (TEM). The thus formed PANI/RGO/Fe3O4 adsorbent was tested and applied in removing Hg(II) in aqueous solution. The initial adsorption rate as well as the adsorption capacity increases with the incorporation of RGO/Fe3O4. The magnetic separation of PANI/RGO/Fe3O4 was easy, and its regeneration can be carried out at the optimal pH of 2. Test results proved the competence of the prepared adsorbent in pollution remediation applications for safer water quality and environmental protection.

Biodegradability of some nitrogenous heterocyclic compounds and co-degradation with phenol by denitrifiers in anoxic sludge reactor.

Phenol and nitrogenous heterocyclic compounds (NHCs) are typical organic pollutants in coal gasification wastewater which are difficult to deal with. Unlike phenol, the stable molecular structure of NHCs make them nearly impossible to degrade under aerobic or anaerobic condition. In this paper, biodegradation of phenol and NHCs as carbon sources for denitrification was studied in a laboratory-scale anoxic reactor. Denitrifiers could degrade 490 mg/L phenol and 321.5 mg/L NO3(-)-N within 12 hours with removal efficiencies of 99.8% and 99.6%, respectively. The inhibition of pyridine on the microbes could be reduced by adding phenol into influent and the experimental results showed that pyridine could be degraded as the sole carbon source with the maximum organic loading rate of 4.38 mg/(g MLSS·h) (MLSS: mixed liquor suspended solids). When phenol was included as a growth substrate, the degradation performance of quinoline and pyrrole was improved due to co-degradation, and removal rate of NHCs increased according with increment of phenol in influent.

Research of iron reduction and the iron reductase localization of anammox bacteria.

The iron-reducing capability of anammox bacteria was examined in this study using Percoll purified anammox bacteria. Anammox bacteria could reduce Fe(III) to Fe(II) with organic matters as the electron donor. The activity of anammox iron-reducing process was dependent on different electron donor, acceptor and pH. The highest iron-reducing activity of anammox bacteria was achieved with Fe(III)-NTA (nitrilotriacetic acid) as electron acceptor and formate as the electron donor at pH7. Similar to other iron reducers, 80 % of the iron reductase in anammox bacteria was located in the membrane fraction. Due to the chemical oxidant of NO2 (-) and the NO3 (-) dependent ferrous iron oxidation by anammox bacteria, the iron-reducing activity of anammox bacteria could be severely inhibited when iron-reducing pathway and the anammox process were coupled. However, the total nitrogen removal efficiency was not significantly affected in the presence of Fe(III). The iron-reducing capability of anammox bacteria could influence both N and Fe cycle on earth, and it is a potential way for wastewater treatment.

Optimal cultivation of simultaneous ammonium and phosphorus removal aerobic granular sludge in A/O/A sequencing batch reactor and the assessment of functional organisms.

In this study, sequencing batch reactor (SBR) with an anaerobic/aerobic/anoxic operating mode was used to culture granular sludge. Optimal adjustment of cycle duration was achieved by the direction ofpH, oxidation reduction potential and dissolved oxygen parameters. The results showed that the treating efficiency was significantly improved as the cycle was shortened from 450 to 360 min and further to 200 min. Nitrogen and phosphorus removal were nearly quantitative after 50 days operation and maintained stable to the end of the study period. The typical cycle tests revealed that simultaneous denitrification and phosphorus removal occurred when aerobic granules were gradually formed. The nitrite effect tests showed that less than 4.8 mg N/L of the nitrite could enhance superficial specific aerobic phosphate uptake rate (SAPUR) under aerobic condition, indicating that the traditional method to evaluate the capability of total phosphate-accumulating organisms (PAOs) was inaccurate. Additionally, a high level of nitrite was detrimental to PAOs. A novel method was developed to determine the activity of each kind of PAOs and other denitrifying organisms. The results showed that (1) nitrate, besides nitrite, could also enhance SAPUR and (2) aerobic granular sludge could perform denitrification even when phosphate was not supplied under anoxic condition, suggesting that other denitrifying organisms besides denitrifying phosphate-accumulating organisms also contributed to denitrification.

Advance nitrogen removal from anaerobic sludge digestion liquor using partial nitrification and denitrification coupled with simultaneous partial nitrification, anammox, and denitrification process.

A novel two-stage continuous-flow partial nitrification and denitrification coupled with simultaneous partial nitrification, anammox, and denitrification (PND-SNAD) process was developed to treat anaerobic sludge digestion liquor. During the stable phase, the total nitrogen and chemical oxygen demand (COD) removal efficiencies were 93 ± 3 % and 59 ± 7 %, respectively. Free ammonia suppression (26.2 ± 12.7 mg/L) and low dissolved oxygen (DO, 0.12 ± 0.07 mg/L) were key factors in the operation of the PND process, while the SNAD process was restricted successfully by limited oxygen (DO < 0.1 mg/L) and short solids retention time (9.7 d). The PND process was an important pretreatment process that could remove biodegradable dissolved COD by denitrification and supply ammonium-oxidizing bacteria (AOB) to the SNAD process. Nitrosomonas and Ca. Brocadia were the dominant AOB and anammox bacteria, respectively. Overall, this research presents a distinctive SNAD combined process for anaerobic sludge digestion liquor treatment.

Fabrication phosphomolybdic acid-reduced graphene oxide nanocomposite by UV photo-reduction and its electrochemical properties.

Phosphomolybdic acid-reduced graphene oxide (PMoA-rGO) nanocomposites are fabricated by a photochemical reduction method. They are characterized by ultraviolet-visible spectra, scanning electron microscope images, Fourier transform infrared spectroscopy, Raman spectra and X-ray photoelectron spectroscopy in order to confirm that oxygen-containing functional groups on GO are replaced by PMoA and that GO is reduced to rGO in the photo-reduction process. The electrochemical properties of PMoA-rGO are investigated by cyclic voltammetry, which shows that the PMoA-rGO modified glassy carbon electrode has high electrocatalytic activity in acid solution via a fast, surface-controlled electron transfer process. The results indicate that the use of rGO not only increases the electroactive surface area, but also facilitates electron transfer due to its high electric conductivity.