Bioreduction of chromate in a syngas-based membrane biofilm reactor.

This study leveraged synthesis gas (syngas), a renewable resource attainable through the gasification of biowaste, to achieve efficient chromate removal from water. To enhance syngas transfer efficiency, a membrane biofilm reactor (MBfR) was employed. Long-term reactor operation showed a stable and high-level chromate removal efficiency > 95%, yielding harmless Cr(III) precipitates, as visualised by scanning electron microscopy and energy dispersive X-ray analysis. Corresponding to the short hydraulic retention time of 0.25 days, a high chromate removal rate of 80 µmol/L/d was attained. In addition to chromate reduction, in situ production of volatile fatty acids (VFAs) by gas fermentation was observed. Three sets of in situ batch tests and two groups of ex situ batch tests jointly unravelled the mechanisms, showing that biological chromate reduction was primarily driven by VFAs produced from in situ syngas fermentation, whereas hydrogen originally present in the syngas played a minor role. 16 S rRNA gene amplicon sequencing has confirmed the enrichment of syngas-fermenting bacteria (such as Sporomusa), who performed in situ gas fermentation leading to the synthesis of VFAs, and organics-utilising bacteria (such as Aquitalea), who utilised VFAs to drive chromate reduction. These findings, combined with batch assays, elucidate the pathways orchestrating synergistic interactions between fermentative microbial cohorts and chromate-reducing microorganisms. The findings facilitate the development of cost-effective strategies for groundwater and drinking water remediation and present an alternative application scenario for syngas.

Early monitoring of pore wetting in membrane distillation using ultrasonic time-domain reflectometry (UTDR).

Pore wetting induced by surfactants and salt scaling is a major obstacle to the industrial application of membrane distillation (MD). Identifying the transition of wetting stages and achieving early monitoring of pore wetting are crucial for wetting control. Herein, we made a pioneering attempt to use ultrasonic time-domain reflectometry (UTDR) technique to non-invasively detect the pore wetting in a direct contact MD, and explain the UTDR waveform with the help of optical coherence tomography (OCT) imaging. The results showed that the water-vapor interface had a strong reflection to ultrasound (reflection coefficient = 0.9995), while the water-membrane and water-scaling layer interfaces showed relatively weak reflection. Therefore, UTDR could effectively detect the movement of water-vapor interface with the low interference from the signals generated by the membrane and scaling layer. For the surfactant-induced wetting, the occurrence of wetting could be successfully detected by the right-shift in phase and the reduction in amplitude of the UTDR waveform. Moreover, the wetting depth could be accurately calculated by the time of flight (ToF) and ultrasonic velocity. For scaling-induced wetting, the waveform slightly shifted to the left at the beginning due to the growth of scaling layer, then to the right because the left-shift was surpassed by the right-shift of the waveform caused by pore wetting. Both for the surfactant- and scaling-induced wetting, the variation of the UTDR waveform was sensitive to wetting dynamics, and the right-shift of phase and the reduction in amplitude of the waveform could act as early monitoring signals to the occurrence of wetting.

Control the hydrophilic layer thickness of Janus membranes by manipulating membrane wetting in membrane distillation.

Janus membranes with asymmetric wettability have attracted wide attentions for their robust anti-oil-wetting/fouling abilities in membrane distillation (MD). Compared to traditional surface modification approaches, in this study, we provided a new approach which manipulated surfactant-induced wetting to fabricate Janus membrane with a controllable thickness of the hydrophilic layer. The membranes with 10, 20, and 40 µm of wetted layers were obtained by stopping the wetting induced by 40 mg L-1 Triton X-100 (J = 25 L m-2 h-1) at about 15, 40, and 120 s, respectively. Then, the wetted layers were coated using polydopamine (PDA) to fabricate the Janus membranes. The resulting Janus membranes showed no significant change in porosities or pore size distributions compared with the virgin PVDF membrane. These Janus membranes exhibited low in-air water contact angles (< 50°), high underwater oil contact angles (> 145°), and low adhesion with oil droplets. Therefore, they all showed excellent oil-water separation performance with ∼100% rejection and stable flux. The Janus membranes showed no significant decline in flux, but a trade-off existed between the hydrophilic layer thicknesses and the vapor flux. Utilizing membranes with tunable hydrophilic layer thickness, we elucidated the underlying mechanism of such trade-off in mass transfer. Furthermore, the successful modification of membranes with different coatings and in-situ immobilization of silver nanoparticles indicated that this facile modification method is universal and can be further expanded for multifunctional membrane fabrication.

Unique Behaviors and Mechanism of Highly Soluble Salt-Induced Wetting in Membrane Distillation.

Scaling-induced wettinggreatly limits the application of membrane distillation (MD) for the desalination of high-salinity feed. Although highly soluble salts (e.g., NaCl) have high concentrations in this water, their scaling-induced wetting remains overlooked. To unravel the elusive wetting behaviors of highly soluble salts, in this study, we systematically investigated the scaling formation and wetting progress by in situ observation with optical coherence tomography (OCT). Through examining the influence of salt type and vapor flux on the wetting behavior, we revealed that highly soluble salt-induced wetting, especially under high vapor flux, shared several unique features: (1) occurring before the bulk feed reached saturation, (2) no scale layer formation observed, and (3) synchronized wetting progress on the millimeter scale. We demonstrated that a moving scale layer caused these interesting phenomena. The initial high vapor flux induced high concentration and temperature polarizations, which led to crystallization at the gas-liquid interface and the formation of an initial scale layer. On the one hand, this scale layer bridged the water into the hydrophobic pores; on the other hand, it blocked the membrane pores and reduced the vapor flux. In this way, the decreased vapor flux mitigated the concentration/temperature polarizations, and consequently led to the dissolution of the feed-facing side of the scale layer. This dissolution prevented the membrane pores from being completely blocked, facilitating the transportation and crystallization of salts at the distillate-facing side of the scale layer (i.e., the gas-liquid interface), thus the proceeding of the wetting layer.

Unraveling the Kinetics and Mechanism of Surfactant-Induced Wetting in Membrane Distillation: An In Situ Observation with Optical Coherence Tomography.

In this study, we performed a direct contact membrane distillation and successfully demonstrated the non-invasive imaging of surfactant-induced wetting using optical coherence tomography. This method enabled us to investigate the wetting kinetics, which was found to follow a "three-region" relationship between the wetting rate and surfactant concentration: the (i) nonwetted region, (ii) concentration-dependent region, and (iii) concentration-independent region at low, intermediate, and high surfactant concentrations, respectively. This wetting behavior was explained by the "autophilic effect", i.e., the wetting was caused by the transfer of surfactants from the water-vapor interface to the unwetted membrane and rendered this membrane hydrophilic, and then the wetting frontier moved forward under capillary forces. At region-(i), the surfactant concentration in the water-vapor interface (Clv) was too low to make the unwetted membrane sufficiently hydrophilic; thereby, the membrane could not be wetted. At region-(ii), due to the fast adsorption of the surfactant on the newly wetted membrane, the wetting rate was determined by the advection/diffusion of surfactants from the feed stream. Consequently, the wetting rate increased with the increases in the water flux and surfactant concentration. At region-(iii), the advection/diffusion provided excess surfactants for adsorption, and thus Clv reached its upper limit (maximum surface excess) and the wetting rate leveled off.

A combination of membrane relaxation and shear stress significantly improve the flux of gravity-driven membrane system.

Gravity-driven membrane (GDM) filtration system is a promising process for decentralized drinking water treatment. During the operation, membrane relaxation and shear stress could be simply achieved by intermittent filtration and water disturbance (created by occasionally shaking membrane model or stirring water in membrane tank), respectively. To better understand the impact of membrane relaxation and shear stress on the biofouling layer and stable flux in GDM system, action of daily 60-min intermission, daily flushing (cross-flow velocity = 10 cm s-1, 1 min), and the combination of the two (flushed right after the 60-min intermission) were compared. The results showed that membrane relaxation and shear stress lonely was ineffective in improving the stable flux, while their combination enhanced the stable flux by 70%. A more open and spatially heterogeneous biofouling layer with a low extracellular polymeric substance (EPS) content and a high microbial activity was formed under the combination of membrane relaxation and shear stress. In-situ optical coherence tomography (OCT) observation revealed that, during intermission, the absence of pushing force by water flow induced a reversible expansion of biofouling layer, and the biofouling layer restored to its initial state soon after resuming filtration. Shear stress caused abrasion and erosion on the biofouling surface, but it exerted little effect on the interior of biofouling layer. Under the combination, however, both the surface and interior of biofouling layer were disturbed because of 1) the water vortexes caused by rough biofouling layer surface, and 2) the porous structure after 60-min intermission. This disturbance, in turn, helped the biofouling layer maintain its roughness and porosity, thereby improving the stable flux of GDM system.

Control of organic and surfactant fouling using dynamic membranes in the separation of oil-in-water emulsions.

HYPOTHESIS: A superhydrophilic membrane with rough and hierarchical structures is possibly fouled by surfactant-stabilized oil and organic foulants, because these foulants could not be hindered by the water layer formed on superhydrophilic membrane surface. A dynamic membrane was possibly an effective method to address this fouling problem. EXPERIMENTS: A microfiltration membrane, a nanofiber membrane, and a dynamic membrane were used for the separation of surfactant-free emulsions, surfactant-stabilized emulsions, and the surfactant-stabilized emulsions containing typical organic foulants. The oil rejection and membrane fouling were compared. FINDINGS: The microfiltration membrane, nanofiber membrane, and dynamic membrane had high resistances to the fouling by surfactant-free emulsions because these membranes were underwater superoleophobic. However, these membranes showed low resistances to the fouling by surfactant-stabilized oil droplets and organic foulants. For the dynamic membrane, the oil droplets and organic foulants trapped in the separation layer could be readily removed in the detachment-washing-recoating steps; therefore, almost no physically irreversible fouling was observed in the multi-cycle filtration. With the size distributions of oil droplets in the emulsions and the particle of the dynamic membrane, the rejection of oil by the dynamic membrane could be calculated by simply assuming that the particle was spherical, uniform, and tightly packed.

Membrane fouling by the aggregations formed from oppositely charged organic foulants.

Due to the lack of robust ways to quantify aggregations, fouling of two-foulant aggregations is poorly understood. This work systematically reports the ultrafiltration membrane fouling by aggregations formed from two oppositely charged organic foulants (i.e., humic acid (HA) and lysozyme (LYS)) with the aid of resonance light scattering (RLS) technique. RLS provides an effective approach to detecting the aggregation concentration and reveals that the HA-LYS aggregations were formed at a mass ratio of m(LYS)/m(HA) = 2.77. During the filtration of the mixture of HA and LYS, aggregations over individual foulants were identified to be the main substances deposited on the membrane surface, where the mass of deposition had a good linear relationship with the feed concentration of the aggregations. The HA-LYS aggregations might decrease the total fouling due to their large size, but reduce the fouling reversibility. In the pH range of 5.5-9.2, the pH value had limiting effects on the concentration of HA-LYS aggregations, as well as the consequent fouling. At low ionic strength, the membrane fouling by HA-LYS aggregations decreased as the ionic strength increased due to the reduction of the aggregation concentration. Oppositely, at high ionic strength, this tendency was reversed due to the electrical double layer compression effect. These results suggest that RLS is a simple and effective way to quantify the aggregations of foulants, and the aggregations of foulants have distinct fouling behaviors compared with the individual foulants.

Effects of water temperature and light intensity on the performance of gravity-driven membrane system.

The selection of favorable environmental conditions for gravity-driven membrane (GDM) systems is crucial to their widespread application. In this study, GDM systems operated under different light intensities (illuminance levels of 0, 200, and 3000 Lux) and water temperatures (10, 20, and 30 °C) were investigated for their performance and fouling layer characteristics. The results showed that indoor light (200 Lux) had limited effects on the performance of the GDM system. However, full daylight (3000 Lux) led to algal growth; these algae increased fouling resistance and deteriorated permeate water by releasing algogenic organic matter, although they could also enhance the heterogeneity of the biofouling layer by increasing the microbial activity. Water temperature rarely influenced the total organic matter removal. The fouling layers had different thicknesses and heterogeneity, but the same level of EPS; therefore, the hydraulic resistances of these fouling layer were almost the same at different water temperatures. These findings suggest that GDM system could be operated at low water temperature and indoor light conditions, and that strong light should be avoided during the operation of GDM systems.

Biofouling in ultrafiltration process for drinking water treatment and its control by chlorinated-water and pure water backwashing.

We investigated biofouling in ultrafiltration (UF) for drinking water treatment and its control by backwashing with chlorinated-water or pure water. By using sodium azide to suppress biological growth, the relative contribution of biofouling to total fouling was estimated, and its value (5.3-56.0%) varied with the feed water, and increased with the increases of filtration time and membrane flux. The biofouling layer could partially remove biodegradable organic matter and ammonia (32.9-74.2%). Backwashing using chlorinated-water partly inactivated the microorganisms (23.8%) but increased the content of extracellular polymeric substances (7.7%) in the biofouling layer. In contrast, backwashing using pure water led to a looser and more porous fouling layer according to optical coherence tomography observation. Consequently, the latter was more effective in reducing fouling resistance (33.41% reduction) compared to backwashing by chlorinated-water (8.6%). These findings reveal the critical roles of biofouling in pollutants removal in addition to membrane permeability, which has important implications for addressing seasonal ammonia pollution.