Surface Microstructure Drives Biofilm Formation and Biofouling of Graphene Oxide Membranes in Practical Water Treatment.

Significant progress has been made previously in the research and development of graphene oxide (GO) membranes for water purification, but their biofouling behavior remains poorly understood. In this study, we investigated the biofilm formation and biofouling of GO membranes with different surface microstructures in the context of filtering natural surface water and for an extended operation period (110 days). The results showed that the relatively hydrophilic and smooth Fe(OH)3/GO membrane shaped a thin and spatially heterogeneous biofilm with high stable flux. However, the ability to simultaneously mitigate biofilm formation and reduce biofouling was not observed in the weakly hydrophilic and wrinkled Fe/GO and H-Fe(OH)3/GO membranes. Microbial analyses revealed that the hydrophilicity and roughness distinguished the bacterial communities and metabolic functions. The organic matter-degrading and predatory bacteria were more adapted to hydrophilic and smooth GO surfaces. These functional taxa were involved in the degradation of extracellular polymeric substances (EPS), and improved biofilm heterogeneity. In contrast, the weakly hydrophilic and wrinkled GO surfaces had reduced biodiversity, while unexpectedly boosting the proliferation of EPS-secreting bacteria, resulting in increased biofilm formation and aggravated biofouling. Moreover, all GO membranes achieved sustainable water purification during the entire operating period.

Purifying surface water contaminated with azo dyes using nanofiltration: Interactions between dyes and dissolved organic matter.

In this research, the interactions of two azo dyes, Methyl Orange (MO) and Eriochrome Black T (EBT), with dissolved organic matter (DOM) in surface water were studied, emphasizing their removal using nano-filtration membranes (NF-270 and NF-90). High-Performance Size Exclusion Chromatography (HPSEC) findings indicated that the dyes' molecular weight in deionized (DI) water ranged from 500 to 15k Dalton (Da), adjusting peak intensities with Jingmi River (JM) water Beijing. Notably, when dyes were diluted in JM water, ultraviolet (UV533 & 466, and UV254), together with total organic carbon (TOC) parameters, revealed color removal rates of 99.49% (EBT), 94.2% (MO), 87.6% DOM removal, and 86% TOC removal for NF-90. The NF-90 membrane demonstrated a 75% flux decline for 50 mL permeate volume due to its finer pore structure and higher rejection effectiveness. In contrast, the NF-270 membrane showed a 60% decline in flux under the same conditions. Attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) analysis of dye-treated membranes in JM water revealed that the NF-270 showed a CC bond peak at 1660 cm-1 across various samples, while analyzing NF-90, the peaks at 1400 cm-1, 1040 cm-1, 750 cm-1, and 620 cm-1 disappeared for composite sample removal. The hydrophobicity of each membrane is measured by the contact angle (CA), which identified that initial CAs for NF-270 and NF-90 were 460 and 700, respectively, that were rapidly declined but stabilized after a few seconds of processing. Overall, this investigation shows that azo dyes interact with DOM in surface waters and enhance the removal efficiency of NF membranes.

The application of chitosan quaternary ammonium salt to replace polymeric aluminum ferric chloride for sewage sludge dewatering.

Inorganic coagulants such as poly aluminum ferric chloride (Al/Fe) are applied conventionally to sewage sludge dewatering and can be retained in the sludge cake, causing its conductivity to increase and generate secondary pollution. To reduce these disadvantages, there is a need to develop alternative, more sustainable chemicals as substitutes for conventional inorganic coagulants. In the present investigation, the application of a polymeric chitosan quaternary ammonium salt (CQAS) is explored as a complete, or partial, replacement for Al/Fe in the context of sludge dewatering processes. Laboratory experiments using digested sewage sludge showed that CQAS could effectively substitute for over 80 % of the Al/Fe inorganic coagulant in the sludge dewatering process. This substitution resulted in a reduction of sludge cake conductivity by more than 50 %. Simulation of sludge dewatering curves and imaging of the sludge surface indicated that the addition of CQAS led to an increase in nanosized pores, and a decrease in the specific resistance of the sludge filter cake as the dosage of Al/Fe decreased to around 30 %. The variations of fluorescence emission, quantum yield and carboxylic and amino groups, suggested that the chelating of Al/Fe decreased due to the bridging effects of CQAS. The CQAS had different flocculation bridging effects on various EPS fractions, which varied the amount of protein chelated with Al/Fe in each fraction. This study provides new information about the benefits of replacing conventional inorganic coagulants with natural organic polymers for sewage sludge dewatering, in terms of reduced sludge cake conductivity and greater dry solids content.

A Reliable Low-Latency Multipath Routing Algorithm for Urban Rail Transit Ad Hoc Networks.

With the advancement of urban rail transit towards intelligence, the demand for urban rail transit communication has increased significantly, but the traditional urban rail transit vehicle-ground communication system has been unable to meet the future vehicle-ground communication requirements. To improve the performance of vehicle-ground communication, the paper proposes a reliable low-latency multipath routing (RLLMR) algorithm for urban rail transit ad hoc networks. First, RLLMR combines the characteristics of urban rail transit ad hoc networks and uses node location information to configure a proactive multipath to reduce route discovery delay. Second, the number of transmission paths is adaptively adjusted according to the quality of service (QoS) requirements for vehicle-ground communication, and then the optimal path is selected based on the link cost function to improve transmission quality. Third, in order to enhance the reliability of communication, a routing maintenance scheme has been added, and the static node-based local repair scheme is used in routing maintenance to reduce the maintenance cost and time. The simulation results show that compared with traditional AODV and AOMDV protocols, the proposed RLLMR algorithm has good performance in improving latency and is slightly inferior to the AOMDV protocol in improving reliability. However, overall, the throughput of the RLLMR algorithm is better than that of the AOMDV.

Marine self-potential measurement tool for autonomous underwater vehicle.

Marine self-potential (SP) measurement is commonly conducted for seafloor sulfide detection and hydrothermal vent studies in deep water using instruments towed close to the seafloor. However, this method has the following shortcomings: (1) It relies on ships for deep towing, and the need for a dedicated ship time lowers its efficiency. (2) Owing to complex topography, most towed instruments are located far from the seafloor to ensure safety, resulting in large effective signal attenuation and low signal-to-noise ratio. (3) The measurement direction is generally a single axis, with only the electric field of the axial component observed, providing limited information. With the gradual maturity of autonomous underwater vehicle (AUV) technology, it has become possible to mount marine SP measurement tools on AUVs for detection. Compared with conventional methods, this method has significant advantages in terms of efficiency, signal-to-noise ratio, and multicomponent observation. The proposed tool is a lightweight underwater device having a compact design and low power consumption, making it suitable for AUVs. The overall volume of the tool is D50 mm × L350 mm, and the underwater weight is 0.6 kg. Chopper amplification technology ensures the low-noise measurement of electric field signals. In addition, the reformed electrodes enhance stability, thereby reducing the mechanical vibration noise. Laboratory test results show that the noise of the data logger is 7.8 nV/rt (Hz)@1 Hz. The marine test conducted in the southwest Indian Ocean verified the reliability of the proposed marine SP measurement tool. The maximum working depth was 4000 m. The test lasted ∼25 h, and the effective electric field data were collected for ∼17 h. This survey found a maximum SP anomaly of 0.55 mV/m in the Yuhuang hydrothermal field, which provided effective data support for the discovery of new seafloor sulfide anomalies.

Understanding point-of-use tap water quality: From instrument measurement to intelligent analysis using sample filtration.

In most cases, point-of-use tap water quality is not routinely monitored due to widely-dispersed sampling sites and the costly tests. Although previous studies have revealed the variation of drinking water quality during distribution in municipal networks, the influence of aging pipes in buildings on quality is still unknown and this makes it difficult for water utilities to conduct regular maintenance. Herein, we have undertaken a survey of tap water samples across 8 districts in Beijing (China) to evaluate the potential effects of pipe age on point-of-use water quality, including turbidity, organic matter characteristics, and bacterial community. By grouping the collected samples according to the pipe age and source water respectively, the results suggested that bacterial diversity is significantly influenced by the pipe age. However, bacterial community structure is clearly influenced by the source water. Similarly, aging pipes in buildings are also responsible for the deterioration of the final water quality, and their effects have been closely linked to selected water quality parameters by evaluating the relevant factors. Moreover, the interrelationships between physico-chemical parameters and bacteria abundance were identified. For example, pH, Ca2+, Mg2+, Na+ and K+ showed a positive relationship with Bacillus abundance. In addition, an intelligent analysis method for understanding pipe age, organic matter concentration, and hardness (i.e., Ca2+ and Mg2+ concentration), based on image analysis of filtered membranes has been developed. The accuracy of prediction was encouraging, but can be improved with the collection of more data from tap water samples. We expect that this method can be exploited by the public to monitor their tap water and provide a feasible and cost-effective approach for water suppliers to locate aging/deteriorating pipes which need to be replaced or maintained.

Identifying active concentrations of biopolymers for enhancing membrane nanofiltration performance: From bench-scale tests to real production considerations.

In the last decades, membrane-based nanofiltration (NF) technique has been widely applied for safe and high-quality drinking water production worldwide. NF membrane fouling has become one of the main obstacles in its application due to high operation cost, and thus numerous efforts have been made. However, there is still a large disconnect between academic findings and their applications. Hence, novel approaches for further exploitation and application are required based on feasibility of implementation. In this work, an optimized design of membrane-based NF plants was proposed, inspired by natural biopolymers present in feed water of NF unit. Specifically, we found beneficial functions of biopolymers, including NF membrane fouling alleviation and effluent quality improvement; these advantages could only be "activated" under a certain concentration range of biopolymers (0-1 mg C/L here), and less or more is not acceptable. This indicated that a NF unit is better to follow a microfiltration (MF) (instead of ultrafiltration (UF) which removes biopolymers) process during which natural biopolymers could be remained; also, this approach is suggested to be valid across different seasons when biopolymers' concentrations could be controlled within an "activated" range by mixing MF and UF permeates. Furthermore, three representative reference biopolymers with different, confirmed spatial structures and molecular weight (MW) were used to elucidate the micro-level functions of natural biopolymers on NF membranes, suggesting that cake layer structures shaped by various biopolymers determine the resulting NF performance. Overall, this innovative proposal is expected to be considered and adopted towards more energy-efficient NF technology for drinking water supply.

Beneficial impacts of natural biopolymers during surface water purification by membrane nanofiltration.

Membrane filtration in various forms has become an increasingly used treatment method worldwide for the supply of safe drinking water. The fouling of membranes is commonly considered to be the major operational limitation to its wider application since it leads to frequent backwashing and a shortening of membrane life, and increased production costs. The components of natural organic matter (NOM) in surface waters have been reported previously to be important foulants of nanofiltration (NF) membranes, however, the potential beneficial effect of particular components of these 'foulants' has not been investigated or demonstrated to date. In this study, we have considered the roles of different organic materials including autochthonous NOM (e.g., biopolymers) and allochthonous NOM (e.g., humic substances) on the fouling of NF membranes by bench-scale tests with samples of two representative source waters (UK) taken in two different seasons (autumn and winter). Microfiltration (MF) and ultrafiltration (UF) were employed to generate two permeates, between which the presence of biopolymers (30 kDa - 90 kDa) is the major difference. We developed sequential filtration (MF/UF-NF) to investigate biopolymers' behaviours in NF process. The results showed that the accumulation of biopolymers on NF membranes can mitigate fouling by providing a protective layer in which medium-low molecular weight (MW) materials (e.g. humic substances) are separated by adsorption and/or size exclusion. The protective layers assisted by biopolymers were seen to be thicker under scanning electron microscope (SEM) observation and characterized by higher roughness (i.e. three-dimensional, spacial structure) and greater adsorptive capacity. Moreover, improvement on NF membrane fouling mitigation could be more significant in autumn, comparing to that in winter. The findings in this study were found to be repeatable in similar tests with samples of comparable raw waters in China, and will be important to the practical application of NF membrane systems in terms of a new approach to combating fouling in long-term operation.

Discovery of Welcome Biopolymers in Surface Water: Improvements in Drinking Water Production.

The presence of biopolymers in surface waters and their significance for potable water supply have received little attention previously owing to their low concentrations. In this paper, we present the results of an extensive study that has investigated the role and benefits of biopolymers during the purification of surface water with reference to their specific biological and physico-chemical properties. Using samples collected from two representative surface waters in China and the United Kingdom, macromolecular biopolymers were separated and concentrated for subsequent investigation of their role in coagulation, metal ion adsorption, and membrane separation. Our results show that biopolymers significantly improve the antifouling capability of membrane nanofiltration, in combination with the enhanced conventional coagulation performance and additional security against several unhealthy metal pollutants (e.g., Fe, Al, and Cr). We believe this is the first study that reveals the versatile benefits and the fate of natural biopolymers in surface water purification processes.

Tracking metal ion-induced organic membrane fouling in nanofiltration by adopting spectroscopic methods: Observations and predictions.

Natural organic matter (NOM) with the size approaching to membrane pore size is commonly considered as the crucial component leading to severe pore blocking and superfluous energy consumption. Aquatic metal ions coexisting with this NOM constituent (target NOM) exert a significant influence on membrane filtration performance; however, little work elucidated their interactions and the impacts on nanofiltration (NF). Therefore, we systematically investigated this issue by titrating three environmentally-relevant metal ions (Al3+, Fe3+ and Cu2+) into the target NOM sample obtained by pre-filtering using NF membrane. Fast spectrophotometric techniques were employed to observe the interactive performance. Results suggested that all metal ions at their critical concentrations caused severe flux decline; Cu2+ at a very low concentration of 5 µM, Al3+ and Fe3+ at 20 µM. NF performance recovered when the concentrations were beyond their critical values, and was improved at excessive concentration when flocs formed. Relationship between spectroscopic characteristics and NF performance was particularly addressed. UV-vis spectrum can be expected to be useful and predictive in membrane fouling control when Al3+ or Fe3+ presented. However, fluorescence fingerprint was not likely that effective since fluorescence intensity continuously reduced with the increasing metal ion concentration, attributed to their quenching effect on NOM fluorophores.

Optimized coagulation pretreatment alleviates ultrafiltration membrane fouling: The role of floc properties and slow-mixing speed on mechanisms of chitosan-assisted coagulation.

To alleviate ultrafiltration (UF) membrane fouling, the pre-coagulation of poly-aluminum chloride (PACl) with the aid of chitosan (CTS) was conducted for synthetic humic acid-kaolin water treatment. Pre-coagulation of three molecular weights (MW) CTSs (50-190 kDa (CTSL), 190-310 kDa (CTSM) and 310-375 kDa (CTSH)) was optimized with slow-mixing speeds of 30, 60 and 90 r/min, respectively. The removal efficiency and floc properties as well as membrane fouling were analyzed, and were compared to results obtained by conventional coagulation with PACl. Results showed that variations in floc properties could be ascribed to the coagulation mechanisms of CTSL/CTSM/CTSH at different slow-mixing speeds, resulting in reduced UF membrane fouling. Specifically, at the low speed of 30 r/min, all three CTS types produced flocs with similar properties, while CTSL resulted in the lowest removal efficiency and aggravated irreversible fouling. At the appropriate speed of 60 r/min, CTSM generated the most compact flocs with the combined effects of bridging and path mechanisms. The compact cake layer formed could alleviate irreversible fouling, which was beneficial for prolonging the operation of the UF membrane. At the high speed of 90 r/min, CTSH formed fragile flocs and aggravated irreversible membrane fouling. We considered membrane fouling to be affected by floc properties and the resultant removal efficiency, which was governed by the MW of the CTS used and the slow-mixing speed applied as well.

Coagulation of surface water: Observations on the significance of biopolymers.

Although the treatment of natural surface waters by coagulation has been investigated extensively, the detailed interaction between natural organic matter and alum is still not adequately understood or predictable, owing to the complexity of different components of the organic matrix and the conditions during coagulation. In this paper, we present the results of a novel approach to the study of the topic, which involved the progressive separation of organic components according to size, followed by coagulation of the filtrate solution, in order to expose the influence of particular organic fractions. Using two natural water sources, representative of lake and river waters, solutions of different organic content were obtained by progressively filtering the source waters using membranes of decreasing pore size; viz. microfiltration (MF), ultrafiltration (UF), and two grades of nanofiltration (NF). While MF had little impact on the range of organics present, UF was able to separate biopolymers (MW > 100 kDa), and NF had a substantially impact on the separation of medium-high MW (1-10 kDa) substances. The results of the coagulation tests showed that the size of flocs was substantially greater when biopolymers were present, suggesting their beneficial role in bridging precipitated Al(OH)3 nanoparticles. For the smaller organic fractions (<10 kDa), the results showed a trend of increasing floc size with decreasing organic MW and concentration, but the trend was minor and may be explained by charge effects. Very similar results were found with both water sources, which support the main finding that biopolymers have an important influence on floc formation.