Zero liquid discharge (ZLD)a wastewater management strategy that eliminates liquid waste and maximizes water usage efficiency has attracted renewed interest worldwide in recent years. Although ...implementation of ZLD reduces water pollution and augments water supply, the technology is constrained by high cost and intensive energy consumption. In this critical review, we discuss the drivers, incentives, technologies, and environmental impacts of ZLD. Within this framework, the global applications of ZLD in the United States and emerging economies such as China and India are examined. We highlight the evolution of ZLD from thermal- to membrane-based processes, and analyze the advantages and limitations of existing and emerging ZLD technologies. The potential environmental impacts of ZLD, notably greenhouse gas emission and generation of solid waste, are discussed and the prospects of ZLD technologies and research needs are highlighted.
Rational design of high-performance stable metal-organic framework (MOF) membranes is challenging, especially for the sustainable treatment of hypersaline waters to address critical global ...environmental issues. Herein, a molecular-level intra-crystalline defect strategy combined with a selective layer thinning protocol is proposed to fabricate robust ultrathin missing-linker UiO-66 (ML-UiO-66) membrane to enable fast water permeation. Besides almost complete salt rejection, high and stable water flux is achieved even under long-term pervaporation operation in hash environments, which effectively addresses challenging stability issues. Then, detailed structural characterizations are employed to identify the type, chemical functionality, and density of intra-crystalline missing-linker defects. Moreover, molecular dynamics simulations shed light on the positive atomistic role of these defects, which are responsible for substantially enhancing structural hydrophilicity and enlarging pore window, consequently allowing ultra-fast water transport via a lower-energy-barrier pathway across three-dimensional sub-nanochannels during pervaporation. Unlike common unfavorable defect effects, the present positive intra-crystalline defect engineering concept at the molecular level is expected to pave a promising way toward not only rational design of next-generation MOF membranes with enhanced permeation performance, but additional water treatment applications.
Mineral scaling is one of the primary factors that constrain the performance of membrane desalination. However, compared to numerous studies on organic and biological fouling, less effort has been ...invested in understanding the mechanisms of mineral scaling. Although anti-fouling membranes have been successfully fabricated to mitigate organic and biological fouling, little progress has been made on the design and fabrication of scaling-resistant membranes. In this review, we discuss the occurrence and consequences of mineral scaling in different membrane desalination processes, and emphasize the complex nature of membrane scaling regulated by feedwater chemistry. We describe established theories associated with mineral scaling, and highlight the knowledge and technology advances in the field of biomineralization that demonstrates the important role of surface chemistry in controlling mineral formation. Current strategies of scaling mitigation are predominantly independent of membrane materials, while the feasibility of developing scaling-resistant membranes has been indicated but not fully achieved in the literature. Accordingly, potential design strategies and challenges associated with the development of novel membrane materials with improved scaling resistance are discussed, and future research needs are proposed.
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•Membrane scaling varies according to feedwater chemistry and desalination technologies.•Surface chemistry regulates mineral formation in biomineralization.•Current strategies of scaling control are dominantly independent of membrane materials.•Membrane scaling can be altered via tuning membrane surface chemistry or topology.•The design of scaling-resistant membrane is challenging due to the complexity of scaling.
We fabricated polyelectrolyte multilayer (PEM) nanofiltration (NF) membranes using a layer-by-layer (LbL) method for effective removal of scale-forming divalent cations (Mg2+, Ca2+, Sr2+, and Ba2+) ...from feedwaters with different salinities. Two polymers with opposite charges, polycation (poly(diallyldimethylammonium chloride), PDADMAC) and polyanion (poly(sodium 4-styrenesulfonate), PSS), were sequentially deposited on a commercial polyamide NF membrane to form a PEM. Compared to pristine and PSS-terminated membranes, PDADMAC-terminated membranes demonstrated much higher rejection of divalent cations and selectivity for sodium transport over divalent cations (Na+/X2+) due to a combination of both Donnan- and size-exclusion effects. A PDADMAC-terminated membrane with 5.5 bilayers exhibited 97% rejection of Mg2+ with selectivity (Na+/Mg2+) greater than 30. We attribute the order of cation rejection (Mg2+ > Ca2+ > Sr2+ > Ba2+) to the ionic size, which governs both the hydration radius and hydration energy of the cations. The ionic strength (salinity) of the feed solution had a significant influence on both water flux and cation rejection of PEM membranes. In feed solutions with high ionic strength, abundant NaCl salt screened the charge of the polyelectrolytes and led to swelling of the multilayers, resulting in decreased selectivity (Na+/X2+) and increased water permeability. The fabricated PEM membranes can be potentially applied to the pretreatment of mild-salinity brackish waters to reduce membrane scaling in the main desalination stage.
•A highly selective PEM membrane was fabricated via the LbL method.•Mg2+, Ca2+, Sr2+, and Ba2+ were used to explore the effect of ionic size on rejection.•Impact of salinity on PEM membrane performance was investigated.•PEM membranes can be applied to control scaling of mild-salinity brackish waters.
Omniphobic membranes are attractive for membrane distillation (MD) because of their superior wetting resistance. However, a design framework for MD membrane remains incomplete, due to the complexity ...of omniphobic membrane fabrication and the lack of fundamental relationship between wetting resistance and water vapor permeability. Here we present a particle-free approach that enables rapid fabrication of monolithic omniphobic membranes for MD desalination. Our monolithic omniphobic membranes display excellent wetting resistance and water purification performance in MD desalination of hypersaline feedwater containing surfactants. We identify that a trade-off exists between wetting resistance and water vapor permeability of our monolithic MD membranes. Utilizing membranes with tunable wetting resistance and permeability, we elucidate the underlying mechanism of such trade-off. We envision that our fabrication method as well as the mechanistic insight into the wetting resistance-vapor permeability trade-off will pave the way for smart design of MD membranes in diverse water purification applications.
We investigated the relationship between membrane surface properties and silica scaling in reverse osmosis (RO). The effects of membrane hydrophilicity, free energy for heterogeneous nucleation, and ...surface charge on silica scaling were examined by comparing thin-film composite polyamide membranes grafted with a variety of polymers. Results show that the rate of silica scaling was independent of both membrane hydrophilicity and free energy for heterogeneous nucleation. In contrast, membrane surface charge demonstrated a strong correlation with the extent of silica scaling (R 2 > 0.95, p < 0.001). Positively charged membranes significantly facilitated silica scaling, whereas a more negative membrane surface charge led to reduced scaling. This observation suggests that deposition of negatively charged silica species on the membrane surface plays a critical role in silica scale formation. Our findings provide fundamental insights into the mechanisms governing silica scaling in reverse osmosis and highlight the potential of membrane surface modification as a strategy to reduce silica scaling.
A novel electrocoagulation membrane reactor (ECMR) was developed, in which ultrafiltration (UF) membrane modules are placed between electrodes to improve effluent water quality and reduce membrane ...fouling. Experiments with feedwater containing clays (kaolinite) and natural organic matter (humic acid) revealed that the combined effect of coagulation and electric field mitigated membrane fouling in the ECMR, resulting in higher water flux than the conventional combination of electrocoagulation and UF in separate units (EC-UF). Higher current densities and weakly acidic pH in the EMCR favored faster generation of large flocs and effectively reduced membrane pore blocking. The hydraulic resistance of the formed cake layers on the membrane surface in ECMR was reduced due to an increase in cake layer porosity and polarity, induced by both coagulation and the applied electric field. The formation of a polarized cake layer was controlled by the applied current density and voltage, with cake layers formed under higher electric field strengths showing higher porosity and hydrophilicity. Compared to EC-UF, ECMR has a smaller footprint and could achieve significant energy savings due to improved fouling resistance and a more compact reactor design.
We investigated the relationship between silica scaling and protein fouling in reverse osmosis (RO). Flux decline caused by combined scaling and fouling was compared with those by individual scaling ...or fouling. Bovine serum albumin (BSA) and lysozyme (LYZ), two proteins with opposite charges at typical feedwater pH, were used as model protein foulants. Our results demonstrate that water flux decline was synergistically enhanced when silica and protein were both present in the feedwater. For example, flux decline after 500 min was far greater in combined silica scaling and BSA fouling experiments (55 ± 6% decline) than those caused by silica (11 ± 2% decline) or BSA (9 ± 1% decline) alone. Similar behavior was observed with silica and LYZ, suggesting that this synergistic effect was independent of protein charge. Membrane characterization by scanning electron microscopy and Fourier transform infrared spectroscopy revealed distinct foulant layers formed by BSA and LYZ in the presence of silica. A combination of dynamic light scattering, transmission electron microscopy , and energy dispersive X-ray spectroscopy analyses further suggested that BSA and LYZ facilitated the formation of aggregates with varied chemical compositions. As a result, BSA and LYZ were likely to play different roles in enhancing flux decline in combined scaling and fouling. Our study suggests that the coexistence of organic foulants, such as proteins, largely alters scaling behavior of silica, and that accurate prediction of RO performance requires careful consideration of foulant–scalant interactions.
Nanostructured titania (nano-TiO2) is produced in diverse shapes, but it remains largely unknown how tuning the morphology of nano-TiO2 may alter its toxicity. Herein, we show that material ...morphology plays a critical role in regulating the phototoxicity of nano-TiO2 to bacteria. Low-dimensional nano-TiO2, including nanotubes, nanorods, and nanosheets, were synthesized hydrothermally, and their effects on the bacterial viability of Escherichia coli and Aeromonas hydrophila were compared to spherical nanostructures (anatase nanospheres and P25). Results reveal that TiO2 nanotubes and nanosheets are less phototoxic than their rod- and sphere-shape counterparts under simulated solar irradiation. None of the tested nano-TiO2 shows toxicity in the dark. In contrast to their diminished phototoxicity, however, TiO2 nanotubes and nanosheets exhibit comparable or even higher photoactivity than other nanostructures. Observations by scanning transmission electron microscopy suggest that material morphology influences nano-TiO2 phototoxicity by governing how nano-TiO2 particles align at the bacterial cell surface. Overall, when comparing materials with different morphologies and dimensionality, nano-TiO2 phototoxicity is not a simple function of photocatalytic reactivity or ROS production. Instead, we propose that the evaluation of nano-TiO2 phototoxicity encompasses a three-pronged approach, involving the intrinsic photoactivity, aggregation of nano-TiO2, and the nano-TiO2/bacteria surface interactions.
The extensive use of nano-TiO2 in industry has led to growing concerns about its potential environmental impacts. However, negligible toxicity is commonly reported under insufficient illumination and ...artificial solution conditions in the literature, which rarely includes discussion of the regulating role of environmental factors. Herein, we report the results of a high-throughput screening assay to evaluate the acute cytotoxicity of six commercial nano-TiO2 materials to Escherichia coli (E. coli) using Lake Michigan water as a model for aquatic surface environments. In particular, we investigate the specific effects of illumination wavelength and natural organic matter (NOM) content. Under simulated solar irradiation, four anatase-based nano-TiO2 materials including Pigment White 6 exhibit significant bacterial toxicity (2 h-IC50 value of 2.7–9.1 mg/L), with toxicity thresholds much lower than previously reported. Negligible toxicity is caused either by pure-phase rutile or under dark condition. Formation of nano-TiO2 aggregates well beyond nano-scale does not eliminate their toxic effect, but photoactivity dominates over the primary size and extent of aggregation in determining the acute cytotoxicity of nano-TiO2. Under visible light irradiation (UVA&B blocked) the antibacterial activity of nano-TiO2 is essentially erased, whereas removing only UVB wavelengths slightly mitigates the toxicity. Suwannee River fulvic acid, acting as a natural dispersant, reverses the extent of nano-TiO2 aggregation, but also reduces its bacterial cytotoxicity. These results demonstrate that despite particle aggregation, the short-term cytotoxicity of nano-TiO2 is predominantly attributed to its phototoxicity, emphasizing the importance of illumination conditions in toxicological screening of photoactive nanomaterials. In the natural aquatic environment, however, this acute toxicity may be mitigated by the attenuation of UV irradiation and increased NOM concentration in the water column.
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► We assess nano-TiO2 toxicity to Escherichia coli by a HTS assay in Lake Michigan water. ► Nano-TiO2 has marked phase- and photo-dependent toxicity regardless of aggregation. ► Photoactivity dominates over primary size & aggregation extent to control TiO2 toxicity. ► Nano-TiO2 toxicity may be mitigated by UV attenuation in natural water. ► SRFA reverses aggregation extent but also reduces the toxicity of nano-TiO2.
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