Pollutant removal and membrane fouling in an anaerobic submerged membrane bioreactor for real sewage treatment.

Real sewage was continuously treated by a laboratory-scale anaerobic submerged membrane bioreactor (AnSMBR) for over 160 days. Results showed that around 90% of chemical oxygen demand, and 99% of turbidity and total suspended solids in the sewage could be removed by the AnSMBR system. Membrane flux sustained at 11 L/(m(2) h) was realized with biogas sparging. Small flocs from sludge deflocculation in the early operational period caused a high membrane fouling rate, and the high specific filtration resistance of the cake layer appeared mostly attributable to the osmotic pressure effect. The performance results were also compared with those in the literature for upflow anaerobic sludge blanket reactors and aerobic membrane bioreactors for sewage treatment, demonstrating that AnSMBR could provide a desirable alternative for sewage treatment.

Superior performance of a membrane bioreactor through innovative in-situ aeration and structural optimization using computational fluid dynamics.

The optimization of membrane bioreactors (MBRs) involves a critical challenge in structural design for mitigation of membrane fouling. To address this issue, a three-dimensional computational fluid dynamics (CFD) model was utilized in this study to simulate the hydrodynamic characteristics of a flat sheet (FS) MBR. The optimization of the membrane module configuration and operating conditions was performed by investigating key parameters that altered the shear stress and liquid velocity. The mixed liquor suspended solids (MLSS) concentration was found to increase the shear stress, leading to a more uniform distribution of shear stress. By optimizing the appropriate bubble diameter to 5 mm, the shear stress on the membrane surface was optimized with relatively uniform distribution. Additionally, extending the side baffle length dramatically improved the uniformity of the shear stress distribution on each membrane. A novel in-situ aeration method was also discovered to promote turbulent kinetic energy by 200 times compared with traditional aeration modes, leading to a more uniform bubble streamline. As a result, the novel in-situ aeration method demonstrated superior membrane antifouling potential in the MBR. This work provides a new approach for the structural design and optimization of MBRs. The innovative combination of the CFD model, optimization techniques, and novel in-situ aeration method has provided a substantial contribution to the advancement of membrane separation technology in wastewater treatment.

High propensity of membrane fouling and the underlying mechanisms in a membrane bioreactor during occurrence of sludge bulking.

While sludge bulking often occurring in activated sludge processes generally leads to serious membrane fouling in membrane bioreactors (MBR), the underlying causes are still unclear. In this study, fouling behaviors of a MBR operated at stages of normal and sludge bulking were compared, and the fouling mechanisms of the different behaviors were explored. It was found that, the MBR could be stably operated in normal stage without membrane cleaning for about 60 days, whereas, daily membrane cleaning had to be carried out when operated in sludge bulking stage. The bulking sludge possessed a rather high specific filtration resistance (SFR) of about 1.36×1014 m·kg-1, which is over 5.33 times than that of the normal sludge. A series of characterizations demonstrated that the bulking sludge had rather lower dewaterability, smaller particle size, higher fractal dimension, higher viscosity, abundant filamentous bacteria and different functional groups of extracellular polymer sustains (EPS). It was suggested that microbial community transition was responsible for the occurrence of sludge bulking, further affecting membrane fouling. Based on these characterizations, it was reported that adhesion propensity (indicated by the thermodynamic interaction) of the bulking sludge to the membrane surface is about 3.6 times than that of the normal sludge. It was proposed that, extra force should be provided to offset a chemical potential gap caused by foulant layer structure transition during sludge bulking in order to sustain filtration of the bulking sludge, resulting in extremely high SFR. This study offered deep thermodynamic mechanisms of MBR fouling during occurrence of sludge bulking.

Effects of polysaccharides' molecular structure on membrane fouling and the related mechanisms.

Fouling behaviors of polysaccharides vary with their structure, while the mechanisms underlying this phenomenon remain unexplored. This work was carried out to explore the thermodynamic fouling mechanisms of polysaccharides with different structure. Carrageenan and xanthan gum were selected as the model polysaccharides with structure of straight and branch chains, respectively. Batch filtration experiments showed that xanthan gum solution corresponded to a more rapid flux decline trend, and specific filtration resistance (SFR) of xanthan gum (2.32 × 1015 m-1 kg-1) was over 10 times than that of carrageenan (2.21 × 1014 m-1 kg-1). It was found that, xanthan gum possessed a more disordered structure and a rather higher viscosity (15.03 mPa·s V.S. 1.98 mPa·s for carrageenan). Calculation of extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory showed higher adhesion energy of xanthan gum (-42.82 my m-2 V.S. -23.26 mJ m-2 for carrageenan). Scanning electron microscopy (SEM) analyses showed that xanthan gum gel layer had a more homogenous structure and rigid polymer backbone, indicating better mixing with water to form a gel. As verified by heating experiments, such a structure tended to contain more bound water. According to this information, Flory-Huggins lattice theory was introduced to build a bridge between polymeric structure and SFR. It was revealed that branch structure corresponded to higher chemical potential change during gel layer formation, and higher ability to carry bound water, resulting in higher filtration resistance during filtration process. This work revealed the fundamental thermodynamic mechanism of membrane fouling caused by polysaccharides with different structure, deepening understanding of membrane fouling.

Preparation of Ni@UiO-66 incorporated polyethersulfone (PES) membrane by magnetic field assisted strategy to improve permeability and photocatalytic self-cleaning ability.

Metal-organic frameworks (MOFs) have been considered as promising nanofillers to fabricate mixed matrix membranes for water treatment. However, manipulating distribution of MOFs nanoparticles in the membrane matrix remains a great challenge. In this study, UiO-66 was firstly coated by magnetic Ni via an in-situ reduction reaction, and then incorporated into polyethersulfone (PES) membrane matrix to prepare PES-Ni@UiO-66 membrane. The magnetic Ni allowed to manipulate the distribution of magnetic Ni@UiO-66 in the phase-inversion process by an external magnetic field. The hydrophilic Ni@UiO-66 can be pulled onto membrane surface by the magnetic force, endowing the prepared membrane with rather higher hydrophilicity. The prepared membrane exhibited superior water permeability with a pure water flux of 611.5 ± 19.8 L·m-2·h-1 and improved antifouling performance. Moreover, benifiting from photocatalytic activity of the exposed Ni@UiO-66 on membrane surface, the obtained PES-Ni@UiO-66 membrane demonstrated excellent photocatalytic self-cleaning ability with a flux recovery rate (FRR) higher than 95% under UV irradiation. Analyzing by extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory indicated that the improved antifouling performance could be attributed to less attractive or even repulsive interaction between the prepared membrane and pollutants. This work provided valuable guidance for structural regulation and development of high-performance MOFs-based membranes for water treatment.

Molecular-level insights into the mitigation of magnesium-natural organic matter induced ultrafiltration membrane fouling by high-dose calcium based on DFT calculation.

While magnesium cation (Mg2+) universally coexists with natural organic matter (NOM) in the water environment, influence of Mg2+ on NOM fouling in membrane filtration process is still unclear. This work was therefore performed to investigate effects of Mg2+ on NOM (sodium alginate (SA) as a model substance) fouling and role of Ca2+ in mitigating fouling from Mg2+ in the ultrafiltration (UF) water treatment process. Filtration tests showed two interesting fouling phenomena: (1) membrane fouling caused by combination of Mg2+ and SA maintained at a high value with the increased Mg2+ concentration; (2) the high fouling property of Mg2+ can be significantly improved by the prominent addition of calcium cation (Ca2+). It was found that changes of foulant morphology played essential roles through thermodynamic mechanisms represented by the Flory-Huggins lattice theory. Density functional theory (DFT) calculation showed that the combination of SA and Mg2+ tends to coordinate two terminal carboxyl groups in SA, beneficial to stretching alginate chains and forming a stable gel network at low doses. In addition, intramolecular coordination is difficult to occur between SA and Mg2+ due to the high hydration repulsion radius of Mg2+. Therefore, a dense and thick gel network remained even under high Mg2+concentration. Furthermore, due to the higher binding affinity of Ca2+ over Mg2+, high doses of Ca2+ trigger a transition of the stable SA-Mg2+ gel network to other configurations where flocculation and aggregation occur, thereby reducing the specific filtration resistance. The proposed thermodynamic mechanism satisfactorily explained the above interesting fouling behaviors, facilitating to development of new solutions to control membrane fouling.

Fundamental thermodynamic mechanisms of membrane fouling caused by transparent exopolymer particles (TEP) in water treatment.

While transparent exopolymer particles (TEP) has high fouling potential, its underlying fouling mechanisms have not yet been well revealed. In current work, fouling characteristics of TEP under different Ca2+ concentrations (0 to 1.5 mM) were investigated. TEP quantification and filtration tests showed that TEP contents increased with Ca2+ concentration, while TEP's specific filtration resistance (SFR) under the influence of Ca2+ concentration presented a unimodal pattern. The peak of TEP's SFR reached at Ca2+ concentration of 1 mM when SA concentration was 0.3 g·L-1. A series of characterizations suggested that microstructure transformation of TEP particles was the main contributor to the resistance variations of TEP solution. The optical microscope observation showed that above and below the critical Ca2+ concentration (1 mM when SA concentration is 0.3 g·L-1 in this study), the formed TEP existed in the form of c-TEP (average particle size is 0.24 µm) and p-TEP (average particle size is 1.05 µm), respectively. Thermodynamic analysis showed that the adhesion ability of c-TEP (-249,989 and - 303,692 kT) was more than 19 times than that of p-TEP (-12,905 kT), which would accelerate foulant layer formation. In addition, below the critical value, the increased SFR with Ca2+ concentration could be explained by integrating Flory-Huggins lattice theory with the preferential intermolecular coordination. Above the critical value, the decreased SFR can be attributed to the formation of a "large-size crack structure" cake layer from the p-TEP. This study revealed fundamental mechanisms of membrane fouling caused by TEP, greatly deepening understanding of TEP fouling, and facilitating to development of effective fouling control strategies.

A novel composite membrane for simultaneous separation and catalytic degradation of oil/water emulsion with high performance.

It is of great significance to develop novel membranes with dual-function of simultaneously separating oil/water emulsion and degrading the contained water-miscible toxic organic components. To meet this requirement, a dual-functional Ni nanoparticles (NPs)@Ag/C-carbon nanotubes (CNTs) composite membrane was fabricated via electroless nickel plating strategy in this study. The as-prepared composite membrane possessed superhydrophilicity with water contact angle of 0° and splendid underwater oleophobic property with oil contact angle of 142°. When the membrane was applied for separation of surfactant stabilized oil-in-water emulsion, high permeate flux (about 97 L m-2·h-1 under gravity), oil rejection (about 98.8%) and antifouling property were achieved. Benefitting from the NiNPs@Ag/C-CNTs layer on membrane surface, the composite membrane exhibited high catalytic degradation activity for water-miscible toxic organic pollutant (4-nitrophenol) with addition of NaBH4 in a flow-through mode. Meanwhile, the NiNPs@Ag/C-CNTs composite membrane possessed excellent durability, which was verified by the good structural integrity even under ultrasonic treatment. The cost-efficiency, high separation and degradation performance of the prepared membrane suggested its great potential for treatment of oily wastewater.

Molecular insights into membrane fouling caused by polysaccharides with different structures in polyaluminum chloride coagulation-ultrafiltration process.

In this study, mechanisms of membrane fouling caused by polysaccharides with different molecular structures in polyaluminum chloride (PACl) coagulation-ultrafiltration (C-UF) process were explored. Carrageenan and xanthan gum were chosen for model foulants of straight chain and branched chain polysaccharides, respectively. Filtration experiments showed that, with PACl dosage of 0-5 mM, specific filtration resistance (SFR) of carrageenan and xanthan solution showed a unimodal pattern and a continuous decrease pattern, respectively. A series of experimental characterizations indicated that the different SFR pattern was closely related to structure of foulants layer. Density functional theory (DFT) calculation suggested that Al3+ preferentially coordinating with the terminal sulfonyl groups of carrageenan chains to promote gel layer formation at low PACl concentration (0.15 mM). There existed a chemical potential gap between bound water in gel layer and free water in the permeate, so that, filtration through gel layer corresponded to rather high SFR for overcoming this gap. In contrast, Al3+ coordinating with the non-terminal sulfonyl groups of carrageenan at high PACl concentration caused transition from gel layer to cake layer, leading to SFR decrease. However, xanthan gum itself can form a dense gel layer with a complex polymer network by virtue of the interlacing of main chains and branches. Al3+ coordinating with the carboxyl groups on branched chains of xanthan gum resulted in clusters of polymer chains and flocculation, corresponding to the reduced SFR. This proposed molecular-level mechanism well explained membrane fouling behaviors of polysaccharides with different molecular structure, and also facilitated to optimize C-UF process for water treatment.

Quantification of interfacial energies associated with membrane fouling in a membrane bioreactor by using BP and GRNN artificial neural networks.

Interfacial energy between sludge foulants and rough membrane surface critically determines adhesive fouling in membrane bioreactors (MBRs). As a current available method, the advanced extensive Derjaguin-Landau-Verwey-Overbeek (XDLVO) approach cannot efficiently quantify the interfacial energy. In this study, novel methods including back propagation (BP) artificial neural network (ANN) and generalized regression neural network (GRNN) were proposed to quantify the interfacial energy associated with the membrane fouling in an MBR. Different levels of 5 apparent input factors and the resulted interfacial energies were used as training and testing databases for establishment of ANN models. The established BP ANN and GRNN models exhibited high regression coefficients and accuracies, suggesting the high capacity of ANN models to capture the complicated non-linear mapping relations between interfacial energy and various factors. As compared with the advanced XDLVO approach, both BP ANN and GRNN showed remarkably improved quantification efficiency. Meanwhile, BP ANN showed better prediction performance than GRNN model. Case study further demonstrated the robustness and feasibility of BP ANN for interfacial energy quantification. This study provided a new approach to quantify interfacial energy associated with membrane fouling.

Membrane fouling caused by biological foams in a submerged membrane bioreactor: Mechanism insights.

Though sludge foaming often occurs and thus causes serious membrane fouling in membrane bioreactors (MBRs), the fouling mechanisms related with the foaming phenomenon have not been well addressed, hindering better understanding and solving foaming problem. In this work, it was interestingly found that, the foulants during the foaming period possessed extremely high specific filtration resistance (SFR) (over 1016 m kg-1) and strong adhesion ability to membrane surface. Chemical characterization showed that the proteins (178.57 mg/L) and polysaccharides (209.21 mg/L) in the foaming sample were about 6.4 times and 5.4 times of those in the supernatant sample, suggesting existence of a mechanism permitting continuous production of these foulants in the MBR during the foaming period. It was revealed that the fouling caused by foams was associated with gel layer filtration process, and the extremely high SFR can be interpreted by chemical potential change in the gel filtration process depicted in Flory-Huggins theory. Meanwhile, analyses by the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory showed that the strong adhesion ability stemmed from the high interaction energy between the foaming foulants and membrane surface. In addition, 16S rDNA gene sequencing identified that the abundance of the foaming related bacteria species in the sludge suspension during the foaming period was more than 10 times of that during the non-foaming period. This study offered new mechanism insights into foaming fouling in MBRs.

A unified thermodynamic mechanism underlying fouling behaviors of soluble microbial products (SMPs) in a membrane bioreactor.

Soluble microbial products (SMPs) are the predominate foulants determining fouling extent in membrane bioreactors (MBRs). However, exact mechanism underlying their typical fouling behaviors remains unrevealed. In this study, the typical fouling behaviors of SMPs during initial operational period of a MBR were characterized. It was found that, although being low content, SMPs rather than sludge particulates preferentially adhered to membrane surface to accumulate a gel layer, and moreover, specific filtration resistance (SFR) of SMPs was approximately 700 times larger than that of the sludge particulates at operational day 3. According to energy balance principle, a unified thermodynamic mechanism underlying these fouling behaviors of SMPs was proposed. Thermodynamic analyses demonstrated that, the attractive interaction energy strength in contact between SMPs and membrane was larger by around 3700 times than that between sludge particulates and membrane, well explaining the extremely high adhesive ability of SMPs over sludge particlulates. Meanwhile, filtration through a SMPs layer was modelled and simulated as a thermodynamic process. Simulation on an agar gel showed that, about 92.6% of SFR was originated from mixing free energy change during filtration. Such a result satisfactorily interpreted the extremely high SFR of SMPs layer over sludge cake layer. The revealed thermodynamic mechanism underlying SMPs fouling behaviors significantly deepened understanding of fouling, and facilitated to development of effective fouling control strategies.

Impacts of morphology on fouling propensity in a membrane bioreactor based on thermodynamic analyses.

Impacts of morphologies of both membrane and foulant on interaction energies related with adhesive fouling in a membrane bioreactor (MBR) were explored by thermodynamic analyses. Interaction energies in three possible interaction scenarios regarding different membrane and foulant morphologies under conditions in this study were quantified according to the thermodynamic methods. It was interestingly found that, strength of total interaction between soluble microbial products (SMPs) and rough membrane was over 20,000 times of that between sludge flocs and rough membrane under same conditions, indicating the extremely higher adhesion ability of SMPs than the large particulate foulants. This result plausibly explained the high fouling propensity of SMPs over sludge flocs. As compared with smooth surfaces, rough surfaces of both membrane and sludge flocs significantly reduced total interaction strength, alleviating adhesive fouling caused by the sludge flocs. Reduce in fractal dimension (Df) of membrane increased adhesive fouling caused by the SMPs, but alleviated adhesive fouling caused by the sludge flocs. These findings gave important implications to better understand and control membrane fouling in MBRs.

Mechanistic insights into alginate fouling caused by calcium ions based on terahertz time-domain spectra analyses and DFT calculations.

Fouling mechanisms underlying the filtration behaviors of alginate solution caused by calcium addition were investigated by Terahertz time-domain spectroscopy (THz-TDS) and density functional theory (DFT) techniques. Filtration tests showed that specific filtration resistance (SFR) of alginate solution (0.75 g L-1) monotonously increased with calcium addition at a relatively low range of calcium concentration (0-1.0 mM), and SFR (2.61 × 1015 m kg-1) of alginate solution with 1.0 mM calcium addition was extremely high as compared with sludge suspension. Characterizations by X-ray photoelectric spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and Thermogravimetric analysis (TGA) showed that the composition of functional groups, elements and thermal stability of alginate was not apparently affected by calcium concentration. Howbeit, THz-TDS spectra showed that calcium addition caused structural variation of alginate polymer in solution. DTF calculation results showed that initial binding of alginate chains induced by calcium ions preferentially occurred in intermolecular other than intramolecular, and moreover, the two alginate chains bridged by a calcium atom tend to stretch in a tetrahedron structure (cross to each other) other than parallel to each other. According to these results, "chemical potential gap" depicted by Flory-Huggins theory was suggested to be responsible for the filtration behaviors of alginate solution caused by calcium addition. This study provided the mechanistic insights into membrane fouling.

Thermodynamic insights into membrane fouling in a membrane bioreactor: Evaluating thermodynamic interactions with Gaussian membrane surface.

While membrane bioreactor (MBR) technology is generally considered as one of the most promising technologies for wastewater treatment and recovery, membrane fouling remains the major obstacle limiting its applications. Interfacial interactions, which critically determine adhesion process and membrane fouling, were investigated in this study. It was found that, natural membrane surface was of a Gaussian surface obeying Gaussian distribution. A Gaussian approach integrating Fourier transform technique, Gaussian distribution and spectrum method was deduced to simulate rough surface topography of membrane. Thereafter, surface element integral (SEI) method, together with composite Simpson rule and triangulation of Gaussian surface was proposed to calculate interfacial interactions. By using the unified method, quantification of interfacial interactions with a Gaussian membrane surface was realized for the first time to date. It was further found that, membrane surface topography had profound impacts on interfacial interactions and adhesive fouling in the MBR. The deduced method can be used to address impacts of various factors on interfacial interactions and adhesive fouling, posing in-depth thermodynamic insights into membrane fouling and pointing towards its widespread potential in fouling research in MBRs.

Membrane fouling in a submerged membrane bioreactor: New method and its applications in interfacial interaction quantification.

Quantification of interfacial interactions between two rough surfaces represents one of the most pressing requirements for membrane fouling prediction and control in membrane bioreactors (MBRs). This study firstly constructed regularly rough membrane and particle surfaces by using rigorous mathematical equations. Thereafter, a new method involving surface element integration (SEI) method, differential geometry and composite Simpson's rule was proposed to quantify the interfacial interactions between the two constructed rough surfaces. This new method were then applied to investigate interfacial interactions in a MBR with the data of surface properties of membrane and foulants experimentally measured. The feasibility of the new method was verified. It was found that asperity amplitude and period of the membrane surface exerted profound effects on the total interaction. The new method had broad potential application fields especially including guiding membrane surface design for membrane fouling mitigation.

Membrane fouling in a submerged membrane bioreactor: An unified approach to construct topography and to evaluate interaction energy between two randomly rough surfaces.

Quantitatively evaluating interaction energy between two randomly rough surfaces is the prerequisite to quantitatively understand and control membrane fouling in membrane bioreactors (MBRs). In this study, a new unified approach to construct rough topographies and to quantify interaction energy between a randomly rough particle and a randomly rough membrane was proposed. It was found that, natural rough topographies of both foulants and membrane could be well constructed by a modified two-variable Weierstrass-Mandelbrot (WM) function included in fractal theory. Spatial differential relationships between two constructed surfaces were accordingly established. Thereafter, a new approach combining these relationships, surface element integration (SEI) approach and composite Simpson's rule was deduced to calculate the interaction energy between two randomly rough surfaces in a submerged MBR. The obtained results indicate the profound effects of surface morphology on interaction energy and membrane fouling. This study provided a basic approach to investigate membrane fouling and interface behaviors.

Influences of fractal dimension of membrane surface on interfacial interactions related to membrane fouling in a membrane bioreactor.

Influences of fractal dimension (Df) of membrane surface on interfacial interactions related to membrane fouling in a membrane bioreactor were investigated based on thermodynamic methods. It was found that membrane surface had significant fractal features, and its fractal dimension could be characterized by the power spectrum method. The modified Weierstrass-Mandelbrot (WM) function was found to be effective to model the fractal membrane surface, and higher Df corresponded to higher number of fine asperities in the modeled surface. Moreover, the modeled surface roughness exponentially decreased with Df. Interaction calculations according to a novel method showed that the interactions for fractal membrane surface were elongated and weakened as compared with smooth membrane surface. It was interestingly found that the absolute value of total interaction monotonically decreased with Df of membrane surface. As Df is a measure of substance stiffness, this result indicates that softer surface is more susceptible to adhesion by sludge foulant. The results offered new insights into membrane fouling mechanisms and alleviation.

Physicochemical correlations between membrane surface hydrophilicity and adhesive fouling in membrane bioreactors.

36 membrane material cases used in membrane bioreactors (MBRs) covering wide range of hydrophilicity/hydrophobicity were used to calculate thermodynamic interactions between membranes and foulants. It was found that adhesive fouling can be represented by the total interaction energy at minimum separation distance (h0). No functional relationship between membrane hydrophilicity and adhesive fouling can be deduced. However, membrane hydrophilicity, in terms of water contact angle or interaction energy between two identical surfaces at h0 in water (ΔGsws), had high statistical correlations with adhesive fouling. This statistical correlations should be attributed to the major role of acid-base interaction in total interaction associated with adhesion in most of membrane cases. Moreover, the statistical correlations were independent of the changes in membrane surface roughness or hydrophilicity/hydrophobicity of foulants. These findings satisfactorily explained the inconsistent conclusions in the literature regarding effects of membrane hydrophilicity on adhesive fouling, giving implications for membrane fouling mitigation.

Influences of acid-base property of membrane on interfacial interactions related with membrane fouling in a membrane bioreactor based on thermodynamic assessment.

Failure of membrane hydrophobicity in predicting membrane fouling requires a more reliable indicator. In this study, influences of membrane acid base (AB) property on interfacial interactions in two different interaction scenarios in a submerged membrane bioreactor (MBR) were studied according to thermodynamic approaches. It was found that both the polyvinylidene fluoride (PVDF) membrane and foulant samples in the MBR had relatively high electron donor (γ(-)) component and low electron acceptor (γ(+)) component. For both of interaction scenarios, AB interaction was the major component of the total interaction. The results showed that, the total interaction monotonically decreased with membrane γ(-), while was marginally affected by membrane γ(+), suggesting that γ(-) could act as a reliable indicator for membrane fouling prediction. This study suggested that membrane modification for fouling mitigation should orient to improving membrane surface γ(-) component rather than hydrophilicity.