Development of combined coagulation-hydrolysis acidification-dynamic membrane bioreactor system for treatment of oilfield polymer-flooding wastewater

• We created a combined system for treating oilfield polymer-flooding wastewater. • The system was composed of coagulation, hydrolysis acidification and DMBR. • Coagulant integrated with demulsifier dominated the removal of crude oil. • The DMBR proceed efficiently without serious membrane fouling. A combined system composed of coagulation, hydrolysis acidification and dynamic membrane bioreactor (DMBR) was developed for treating the wastewater produced from polymer flooding. Performance and mechanism of the combined system as well as its respective units were also evaluated. The combined system has shown high-capacity to remove all contaminants in the influent. In this work, the coagulant, polyacrylamide-dimethyldiallyammonium chloride-butylacrylate terpolymer (P(DMDAAC-AM-BA)), integrated with demulsifier (SD-46) could remove 91.8% of crude oil and 70.8% of COD. Hydrolysis acidification unit improved the biodegradability of the influent and the experimental results showed that the highest acidification efficiency in hydrolysis acidification reactor was 20.36% under hydraulic retention time of 7 h. The DMBR proceeded efficiently without serious blockage process of membrane fouling, and the concentration of ammonia nitrogen (NH₃-N), oil, chemical oxygen demand and biological oxygen demand in effluent were determined to be 3.4±2.1, 0.3±0.6, 89.7±21.3 and 13±4.7 mg/L.     

Enhanced cross-flow filtration with flat-sheet ceramic membranes by titanium-based coagulation for membrane fouling control

• Ceramic membrane filtration showed high performance for surface water treatment. • PTC pre-coagulation could enhance ceramic membrane filtration performance. • Ceramic membrane fouling was investigated by four varied mathematical models. • PTC pre-coagulation was high-effective for ceramic membrane fouling control. Application of ceramic membrane (CM) with outstanding characteristics, such as high flux and chemical-resistance, is inevitably restricted by membrane fouling. Coagulation was an economical and effective technology for membrane fouling control. This study investigated the filtration performance of ceramic membrane enhanced by the emerging titanium-based coagulant (polytitanium chloride, PTC). Particular attention was paid to the simulation of ceramic membrane fouling using four widely used mathematical models. Results show that filtration of the PTC-coagulated effluent using flat-sheet ceramic membrane achieved the removal of organic matter up to 78.0%. Permeate flux of ceramic membrane filtration reached 600 L/(m²·h), which was 10-fold higher than that observed with conventional polyaluminum chloride (PAC) case. For PTC, fouling of the ceramic membrane was attributed to the formation of cake layer, whereas for PAC, standard filtration/intermediate filtration (blocking of membrane pores) was also a key fouling mechanism. To sum up, cross-flow filtration with flat-sheet ceramic membranes could be significantly enhanced by titanium-based coagulation to produce both high-quality filtrate and high-permeation flux.     

Excitation-emission matrix (EEM) fluorescence spectroscopy for characterization of organic matter in membrane bioreactors: Principles,methods and applications

• Principles and methods for fluorescence EEM are systematically outlined. • Fluorophore peak/region/component and energy information can be extracted from EEM. • EEM can fingerprint the physical/chemical/biological properties of DOM in MBRs. • EEM is useful for tracking pollutant transformation and membrane retention/fouling. • Improvements are still needed to overcome limitations for further studies. The membrane bioreactor (MBR) technology is a rising star for wastewater treatment. The pollutant elimination and membrane fouling performances of MBRs are essentially related to the dissolved organic matter (DOM) in the system. Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy, a powerful tool for the rapid and sensitive characterization of DOM, has been extensively applied in MBR studies; however, only a limited portion of the EEM fingerprinting information was utilized. This paper revisits the principles and methods of fluorescence EEM, and reviews the recent progress in applying EEM to characterize DOM in MBR studies. We systematically introduced the information extracted from EEM by considering the fluorescence peak location/intensity, wavelength regional distribution, and spectral deconvolution (giving fluorescent component loadings/scores), and discussed how to use the information to interpret the chemical compositions, physiochemical properties, biological activities, membrane retention/fouling behaviors, and migration/transformation fates of DOM in MBR systems. In addition to conventional EEM indicators, novel fluorescent parameters are summarized for potential use, including quantum yield, Stokes shift, excited energy state, and fluorescence lifetime. The current limitations of EEM-based DOM characterization are also discussed, with possible measures proposed to improve applications in MBR monitoring.     

Surface modification of mesoporous silica nanoparticle with 4-triethoxysilylaniline to enhance seawater desalination properties of thin-film nanocomposite reverse osmosis membranes

• Mesoporous silica nanoparticle was modified with 4-triethoxysilylaniline. • AMSN-based TFN-RO membranes were prepared for seawater desalination. • Water transport capability of the AMSN was limited by polyamide. • Polyamide still plays a key role in permeability of the TFN RO membranes. Mesoporous silica nanoparticles (MSN), with higher water permeability than NaA zeolite, were used to fabricate thin-film nanocomposite (TFN) reverse osmosis (RO) membranes. However, only aminoalkyl-modified MSN and low-pressure (less than 2.1 MPa) RO membrane were investigated. In this study, aminophenyl-modified MSN (AMSN) were synthesized and used to fabricate high-pressure (5.52 MPa) RO membranes. With the increasing of AMSN dosage, the crosslinking degree of the aromatic polyamide decreased, while the hydrophilicity of the membranes increased. The membrane morphology was maintained to show a ridge-and-valley structure, with only a slight increase in membrane surface roughness. At the optimum conditions (AMSN dosage of 0.25 g/L), when compared with the pure polyamide RO membrane, the water flux of the TFN RO membrane (55.67 L/m²/h) was increased by about 21.6%, while NaCl rejection (98.97%) was slightly decreased by only 0.29%. However, the water flux of the membranes was much lower than expected. We considered that the enhancement of RO membrane permeability is attributed to the reduction of the effective thickness of the PA layer.     

Response of bioaerosol cells to photocatalytic inactivation with ZnO and TiO2 impregnated onto Perlite and Poraver carriers

•ZnO/Perlite inactivated 72% of bioaerosols in continuous gas phase. •TiO₂ triggered the highest level of cytotoxicity with 95% dead cells onto Poraver. •Inactivation mechanism occurred by membrane damage, morphological changes and lysis. •ZnO/Poraver showed null inactivation of bioaerosols. •Catalysts losses at the outlet of the photoreactor for all systems were negligible. Bioaerosols are airborne microorganisms that cause infectious sickness, respiratory and chronic health issues. They have become a latent threat, particularly in indoor environment. Photocatalysis is a promising process to inactivate completely bioaerosols from air. However, in systems treating a continuous air flow, catalysts can be partially lost in the gaseous effluent. To avoid such phenomenon, supporting materials can be used to fix catalysts. In the present work, four photocatalytic systems using Perlite or Poraver glass beads impregnated with ZnO or TiO₂ were tested. The inactivation mechanism of bioaerosols and the cytotoxic effect of the catalysts to bioaerosols were studied. The plug flow photocatalytic reactor treated a bioaerosol flow of 460×1 0⁶ cells/m³_air with a residence time of 5.7 s. Flow Cytometry (FC) was used to quantify and characterize bioaerosols in terms of dead, injured and live cells. The most efficient system was ZnO/Perlite with 72% inactivation of bioaerosols, maintaining such inactivation during 7.5 h due to the higher water retention capacity of Perlite (2.8 mL/g_Perlite) in comparison with Poraver (1.5 mL/g_Perlite). However, a global balance showed that TiO₂/Poraver system triggered the highest level of cytotoxicity to bioaerosols retained on the support after 96 h with 95% of dead cells. SEM and FC analyses showed that the mechanism of inactivation with ZnO was based on membrane damage, morphological cell changes and cell lysis; whereas only membrane damage and cell lysis were involved with TiO₂. Overall, results highlighted that photocatalytic technologies can completely inactivate bioaerosols in indoor environments.     

Fate of microplastics in a coastal wastewater treatment plant: Microfibers could partially break through the integrated membrane system

• Fate of microplastics in integrated membrane system for water reuse was investigated. • Integrated membrane system has high removal efficiency (>98%) for microplastics. • Microplastics (>93%) were mainly removed through membrane bioreactor treatment. • Small scale fiber plastics (<200 μm) could break through reverse osmosis (RO) system. • The flux of microplastics maintained at 2.7 × 10¹¹ MPs/d after the RO treatment. Rare information on the fate of microplastics in the integrated membrane system (IMS) system in full-scale wastewater treatment plant was available. The fate of microplastics in IMS in a coastal reclaimed water plant was investigated. The removal rate of microplastics in the IMS system reached 93.2% after membrane bioreactor (MBR) treatment while that further increased to 98.0% after the reverse osmosis (RO) membrane process. The flux of microplastics in MBR effluent was reduced from 1.5 × 10¹³ MPs/d to 10.2 × 10¹¹ MPs/d while that of the RO treatment decreased to 2.7 × 10¹¹ MPs/d. Small scale fiber plastics (<200 μm) could break through RO system according to the size distribution analysis. The application of the IMS system in the reclaimed water plant could prevent most of the microplastics from being discharged in the coastal water. These findings suggested that the IMS system was more efficient than conventional activated sludge system (CAS) for the removal of microplastics, while the discharge of small scale fiber plastics through the IMS system should also not be neglected because small scale fiber plastics (<200 μm) could break through IMS system equipped with the RO system.     

Membrane-based treatment of shale oil and gas wastewater: The current state of knowledge

• Shale oil and gas production generates wastewater with complex composition. • Membrane technologies emerged for the treatment of shale oil and gas wastewater. • Membrane technologies should tolerate high TDS and consume low primary energy. • Pretreatment is a key component of integrated wastewater treatment systems. • Full-scale implementation of membrane technologies is highly desirable. Shale oil and gas exploitation not only consumes substantial amounts of freshwater but also generates large quantities of hazardous wastewater. Tremendous research efforts have been invested in developing membrane-based technologies for the treatment of shale oil and gas wastewater. Despite their success at the laboratory scale, membrane processes have not been implemented at full scale in the oil and gas fields. In this article, we analyze the growing demands of wastewater treatment in shale oil and gas production, and then critically review the current stage of membrane technologies applied to the treatment of shale oil and gas wastewater. We focus on the unique niche of those technologies due to their advantages and limitations, and use mechanical vapor compression as the benchmark for comparison. We also highlight the importance of pretreatment as a key component of integrated treatment trains, in order to improve the performance of downstream membrane processes and water product quality. We emphasize the lack of sufficient efforts to scale up existing membrane technologies, and suggest that a stronger collaboration between academia and industry is of paramount importance to translate membrane technologies developed in the laboratory to the practical applications by the shale oil and gas industry.     

Electro-assisted CNTs/ceramic flat sheet ultrafiltration membrane for enhanced antifouling and separation performance

• A stable and electroconductive CNTs/ceramic membrane was fabricated. • The membrane with the electro-assistance exhibited optimal fouling mitigation. • The removal efficiency was improved by the -2.0 V electro-assistance. • Electro-assisted filtration is energy-saving than that of commercial membrane. Ultrafiltration is employed as an important process for water treatment and reuse, which is of great significance to alleviate the shortage of water resources. However, it suffers from severe membrane fouling and the trade-off between selectivity and permeability. In this work, a CNTs/ceramic flat sheet ultrafiltration membrane coupled with electro-assistance was developed for improving the antifouling and separation performance. The CNTs/ceramic flat sheet membrane was fabricated by coating cross-linked CNTs on ceramic membrane, featuring a good electroconductivity of 764.75 S/m. In the filtration of natural water, the permeate flux of the membrane with the cell voltage of -2.0 V was 1.8 times higher than that of the membrane without electro-assistance and 5.7-fold greater than that of the PVDF commercial membrane. Benefiting from the electro-assistance, the removal efficiency of the typical antibiotics was improved by 50%. Furthermore, the electro-assisted membrane filtration process showed 70% reduction in energy consumption compared with the filtration process of the commercial membrane. This work offers a feasible approach for membrane fouling mitigation and effluent quality improvement and suggests that the electro-assisted CNTs/ceramic membrane filtration process has great potential in the application of water treatment.     

Using loose nanofiltration membrane for lake water treatment: A pilot study

• A pilot study was conducted for drinking water treatment using loose NF membranes. • The membranes had very high rejection of NOM and medium rejection of Ca²⁺/Mg²⁺. • Organic fouling was dominant and contribution of inorganic fouling was substantial. • Both organic and inorganic fouling had spatial non-uniformity on membrane surface. • Applying EDTA at basic conditions was effective in removing membrane fouling. Nanofiltration (NF) using loose membranes has a high application potential for advanced treatment of drinking water by selectively removing contaminants from the water, while membrane fouling remains one of the biggest problems of the process. This paper reported a seven-month pilot study of using a loose NF membrane to treat a sand filtration effluent which had a relatively high turbidity (~0.4 NTU) and high concentrations of organic matter (up to 5 mg/L as TOC), hardness and sulfate. Results showed that the membrane demonstrated a high rejection of TOC (by>90%) and a moderately high rejection of two pesticides (54%–82%) while a moderate rejection of both calcium and magnesium (~45%) and a low rejection of total dissolved solids (~27%). The membrane elements suffered from severe membrane fouling, with the membrane permeance decreased by 70% after 85 days operation. The membrane fouling was dominated by organic fouling, while biological fouling was moderate. Inorganic fouling was mainly caused by deposition of aluminum-bearing substances. Though inorganic foulants were minor contents on membrane, their contribution to overall membrane fouling was substantial. Membrane fouling was not uniform on membrane. While contents of organic and inorganic foulants were the highest at the inlet and outlet region, respectively, the severity of membrane fouling increased from the inlet to the outlet region of membrane element with a difference higher than 30%. While alkaline cleaning was not effective in removing the membrane foulants, the use of ethylenediamine tetraacetate (EDTA) at alkaline conditions could effectively restore the membrane permeance.     

An antifouling catechol/chitosan-modified polyvinylidene fluoride membrane for sustainable oil-in-water emulsions separation

• Underwater superoleophobic membrane was fabricated by deposition of catechol/chitosan. • The membrane had ultrahigh pure water flux and was stable under harsh pH conditions. • The membrane exhibited remarkable antifouling property in O/W emulsion separation. • The hydration layer on the membrane surface prevented oil droplets adhesion. Low-pressure membrane filtrations are considered as effective technologies for sustainable oil/water separation. However, conventional membranes usually suffer from severe pore clogging and surface fouling, and thus, novel membranes with superior wettability and antifouling features are urgently required. Herein, we report a facile green approach for the development of an underwater superoleophobic microfiltration membrane via one-step oxidant-induced ultrafast co-deposition of naturally available catechol/chitosan on a porous polyvinylidene fluoride (PVDF) substrate. Membrane morphology and surface chemistry were studied using a series of characterization techniques. The as-prepared membrane retained the original pore structure due to the ultrathin and uniform catechol/chitosan coating. It exhibited ultrahigh pure water permeability and robust chemical stability under harsh pH conditions. Moreover, the catechol/chitosan hydrophilic coating on the membrane surface acting as an energetic barrier for oil droplets could minimize oil adhesion on the surface, which endowed the membrane with remarkable antifouling property and reusability in a cyclic oil-in-water (O/W) emulsion separation. The modified membrane exhibited a competitive flux of ~428 L/(m²·h·bar) after three filtration cycles, which was 70% higher than that of the pristine PVDF membrane. These results suggest that the novel underwater superoleophobic membrane can potentially be used for sustainable O/W emulsions separation, and the proposed green facile modification approach can also be applied to other water-remediation materials considering its low cost and simplicity.     

Metabolic uncoupler, 3,3′,4′,5-tetrachlorosalicylanilide addition for sludge reduction and fouling control in a gravity-driven membrane bioreactor

• Effects of metabolic uncoupler TCS on the performances of GDMBR were evaluated. • Sludge EPS reduced and transformed into dissolved SMP when TCS was added. • Appropriate TCS increased the permeability and reduced cake layer fouling. • High dosage aggravated fouling due to compact cake layer with low bio-activity. The gravity-driven membrane bioreactor (MBR)system is promising for decentralized sewage treatment because of its low energy consumption and maintenance requirements. However, the growing sludge not only increases membrane fouling, but also augments operational complexities (sludge discharge). We added the metabolic uncoupler 3,3′,4′,5-tetrachlorosalicylanilide (TCS) to the system to deal with the mentioned issues. Based on the results, TCS addition effectively decreased sludge ATP and sludge yield (reduced by 50%). Extracellular polymeric substances (EPS; proteins and polysaccharides) decreased with the addition of TCS and were transformed into dissolved soluble microbial products (SMPs) in the bulk solution, leading to the break of sludge flocs into small fragments. Permeability was increased by more than two times, reaching 60–70 L/m²/h bar when 10–30 mg/L TCS were added, because of the reduced suspended sludge and the formation of a thin cake layer with low EPS levels. Resistance analyses confirmed that appropriate dosages of TCS primarily decreased the cake layer and hydraulically reversible resistances. Permeability decreased at high dosage (50 mg/L) due to the release of excess sludge fragments and SMP into the supernatant, with a thin but more compact fouling layer with low bioactivity developing on the membrane surface, causing higher cake layer and pore blocking resistances. Our study provides a fundamental understanding of how a metabolic uncoupler affects the sludge and bio-fouling layers at different dosages, with practical relevance for in situ sludge reduction and membrane fouling alleviation in MBR systems.     

Locally enhanced electric field treatment (LEEFT) for water disinfection

• Nanowire-assisted LEEFT is applied for water disinfection with low voltages. • LEEFT inactivates bacteria by disrupting cell membrane through electroporation. • Multiple electrodes and device configurations have been developed for LEEFT. • The LEEFT is low-cost, highly efficient, and produces no DBPs. • The LEEFT can potentially be applicable for water disinfection at all scales. Water disinfection is a critical step in water and wastewater treatment. The most widely used chlorination suffers from the formation of carcinogenic disinfection by-products (DBPs) while alternative methods (e.g., UV, O₃, and membrane filtration) are limited by microbial regrowth, no residual disinfectant, and high operation cost. Here, a nanowire-enabled disinfection method, locally enhanced electric field treatment (LEEFT), is introduced with advantages of no chemical addition, no DBP formation, low energy consumption, and efficient microbial inactivation. Attributed to the lightning rod effect, the electric field near the tip area of the nanowires on the electrode is significantly enhanced to inactivate microbes, even though a small external voltage (usually<5 V) is applied. In this review, after emphasizing the significance of water disinfection, the theory of the LEEFT is explained. Subsequently, the recent development of the LEEFT technology on electrode materials and device configurations are summarized. The disinfection performance is analyzed, with respect to the operating parameters, universality against different microorganisms, electrode durability, and energy consumption. The studies on the inactivation mechanisms during the LEEFT are also reviewed. Lastly, the challenges and future research of LEEFT disinfection are discussed.     

Forward osmosis coupled with lime-soda ash softening for volume minimization of reverse osmosis concentrate and CaCO3 recovery: A case study on the coal chemical industry

• Forward osmosis (FO) coupled with chemical softening for CCI ROC minimization • Effective removal of scale precursor ions by lime-soda ash softening • Enhanced water recovery from 54% to 86% by mitigation of FO membrane scaling • High-purity CaCO₃ was recovered from the softening sludge • Membrane cleaning efficiency of 88.5% was obtained by EDTA for softened ROC Reverse osmosis (RO) is frequently used for water reclamation from treated wastewater or desalination plants. The RO concentrate (ROC) produced from the coal chemical industry (CCI) generally contains refractory organic pollutants and extremely high-concentration inorganic salts with a dissolved solids content of more than 20 g/L contributed by inorganic ions, such as Na⁺, Ca²⁺, Mg²⁺, Cl⁻, and SO₄²⁻. To address this issue, in this study, we focused on coupling forward osmosis (FO) with chemical softening (FO-CS) for the volume minimization of CCI ROC and the recovery of valuable resources in the form of CaCO₃. In the case of the real raw CCI ROC, softening treatment by lime-soda ash was shown to effectively remove Ca²⁺/Ba²⁺ (>98.5%) and Mg²⁺/Sr²⁺/Si (>80%), as well as significantly mitigate membrane scaling during FO. The softened ROC and raw ROC corresponded to a maximum water recovery of 86% and 54%, respectively. During cyclic FO tests (4 × 10 h), a 27% decline in the water flux was observed for raw ROC, whereas only 4% was observed for softened ROC. The cleaning efficiency using EDTA was also found to be considerably higher for softened ROC (88.5%) than that for raw ROC (49.0%). In addition, CaCO₃ (92.2% purity) was recovered from the softening sludge with an average yield of 5.6 kg/m³ treated ROC. This study provides a proof-of-concept demonstration of the FO-CS coupling process for ROC volume minimization and valuable resources recovery, which makes the treatment of CCI ROC more efficient and more economical.     

Performance of activated carbon coated graphite bipolar electrodes on capacitive deionization method for salinity reduction

• Graphite bipolar electrodes act as an appropriate bed for the CDI process. • Activated carbon Coating improves the application of the electrodes. • CDI is an environmentally friendly method to apply for brackish water. • Initial concentration is the most important parameter in the CDI method. • CDI process in a batch-mode setup needs more development. This research investigates a capacitive deionization method for salinity reduction in a batch reactor as a new approach for desalination. Reductions of cost and energy compared with conventional desalination methods are the significant advantages of this approach. In this research, experiments were performed with a pair of graphite bipolar electrodes that were coated with a one-gram activated carbon solution. After completing preliminary tests, the impacts of four parameters on electrical conductivity reduction, including (1) the initial concentration of feed solution, (2) the duration of the tests, (3) the applied voltage, and (4) the pH of the solution, were examined. The results show that the maximum efficiency of electrical conductivity reduction in this laboratory-scale reactor is about 55%. Furthermore, the effects of the initial concentration of feed solution are more significant than the other parameters. Thus, using the capacitive deionization method for water desalination with low and moderate salt concentrations (i.e., brackish water) is proposed as an affordable method. Compared with conventional desalination methods, capacitive deionization is not only more efficient but also potentially more environmentally friendly.     

Techno-economic characteristics of wastewater treatment plants retrofitted from the conventional activated sludge process to the membrane bioreactor process

• Retrofitting from CAS to MBR increased effluent quality and environmental benefits. • Retrofitting from CAS to MBR increased energy consumption but not operating cost. • Retrofitting from CAS to MBR increased the net profit and cost efficiency. • The advantage of MBR is related to the adopted effluent standard. • The techno-economy of MBR improves with stricter effluent standards. While a growing number of wastewater treatment plants (WWTPs) are being retrofitted from the conventional activated sludge (CAS) process to the membrane bioreactor (MBR) process, the debate on the techno-economy of MBR vs. CAS has continued and calls for a thorough assessment based on techno-economic valuation. In this study, we analyzed the operating data of 20 large-scale WWTPs (capacity≥10000 m³/d) and compared their techno-economy before and after the retrofitting from CAS to MBR. Through cost-benefit analysis, we evaluated the net profit by subtracting the operating cost from the environmental benefit (estimated by the shadow price of pollutant removal and water reclamation). After the retrofitting, the removal rate of pollutants increased (e.g., from 89.0% to 93.3% on average for NH₃-N), the average energy consumption increased from 0.40 to 0.57 kWh/m³, but the operating cost did not increase significantly. The average marginal environmental benefit increased remarkably (from 0.47 to 0.66 CNY/g for NH₃-N removal), leading to an increase in the average net profit from 19.4 to 24.4 CNY/m³. We further scored the technical efficiencies via data envelopment analysis based on non-radial directional distance functions. After the retrofitting, the relative cost efficiency increased from 0.70 to 0.73 (the theoretical maximum is 1), while the relative energy efficiency did not change significantly. The techno-economy is closely related to the effluent standard adopted, particularly when truncating the extra benefit of pollutant removal beyond the standard in economic modeling. The modeling results suggested that MBR is more profitable than CAS given stricter effluent standards.     

TiO2@palygorskite composite for the efficient remediation of oil spills via a dispersion-photodegradation synergy

• A novel and multi-functional clay-based oil spill remediation system was constructed. • TiO₂@PAL functions as a particulate dispersant to break oil slick into tiny droplets. • Effective dispersion leads to the direct contact of TiO₂ with oil pollutes directly. • TiO₂ loaded on PAL exhibits efficient photodegradation for oil pollutants. • TiO₂@PAL shows a typical dispersion-photocatalysis synergistic remediation. Removing spilled oil from the water surface is critically important given that oil spill accidents are a common occurrence. In this study, TiO₂@Palygorskite composite prepared by a simple coprecipitation method was used for oil spill remediation via a dispersion-photodegradation synergy. Diesel could be efficiently dispersed into small oil droplets by TiO₂@Palygorskite. These dispersed droplets had an average diameter of 20–30 mm and exhibited good time stability. The tight adsorption of TiO₂@Palygorskite on the surface of the droplets was observed in fluorescence and SEM images. As a particulate dispersant, the direct contact of TiO₂@Palygorskite with oil pollutants effectively enhanced the photodegradation efficiency of TiO₂ for oil. During the photodegradation process, •O₂⁻and •OH were detected by ESR and radical trapping experiments. The photodegradation efficiency of diesel by TiO₂@Palygorskite was enhanced by about 5 times compared with pure TiO₂ under simulated sunlight irradiation. The establishment of this new dispersion-photodegradation synergistic remediation system provides a new direction for the development of marine oil spill remediation.     

Sludge fermentation liquid addition attained advanced nitrogen removal in low C/N ratio municipal wastewater through short-cut nitrification-denitrification and partial anammox

• Sludge fermentation liquid addition resulted in a high NAR of 97.4%. • Extra NH₄⁺-N from SFL was removed by anammox in anoxic phase. • Nitrogen removal efficiency of 92.51% was achieved in municipal wastewater. • The novel system could efficiently treat low COD/N municipal wastewater. Biological nitrogen removal of wastewater with low COD/N ratio could be enhanced by the addition of wasted sludge fermentation liquid (SFL), but the performance is usually limited by the introducing ammonium. In this study, the process of using SFL was successfully improved by involving anammox process. Real municipal wastewater with a low C/N ratio of 2.8–3.4 was treated in a sequencing batch reactor (SBR). The SBR was operated under anaerobic-aerobic-anoxic (AOA) mode and excess SFL was added into the anoxic phase. Stable short-cut nitrification was achieved after 46d and then anammox sludge was inoculated. In the stable period, effluent total inorganic nitrogen (TIN) was less than 4.3 mg/L with removal efficiency of 92.3%. Further analysis suggests that anammox bacteria, mainly affiliated with Candidatus_Kuenenia, successfully reduced the external ammonia from the SFL and contributed approximately 28%–43% to TIN removal. Overall, this study suggests anammox could be combined with SFL addition, resulting in a stable enhanced nitrogen biological removal.     

Mechanism of dichloromethane disproportionation over mesoporous TiO2 under low temperature

• Mechanism of DCM disproportionation over mesoporous TiO₂ was studied. • DCM was completely eliminated at 350℃ under 1 vol.% humidity. • Anatase (001) was the key for disproportionation. • A competitive oxidation route co-existed with disproportionation. • Disproportionation was favored at low temperature. Mesoporous TiO₂ was synthesized via nonhydrolytic template-mediated sol-gel route. Catalytic degradation performance upon dichloromethane over as-prepared mesoporous TiO₂, pure anatase and rutile were investigated respectively. Disproportionation took place over as-made mesoporous TiO₂ and pure anatase under the presence of water. The mechanism of disproportionation was studied by in situ FTIR. The interaction between chloromethoxy species and bridge coordinated methylenes was the key step of disproportionation. Formate species and methoxy groups would be formed and further turned into carbon monoxide and methyl chloride. Anatase (001) played an important role for disproportionation in that water could be dissociated into surface hydroxyl groups on such structure. As a result, the consumed hydroxyl groups would be replenished. In addition, there was another competitive oxidation route governed by free hydroxyl radicals. In this route, chloromethoxy groups would be oxidized into formate species by hydroxyl radicals transfering from the surface of TiO₂. The latter route would be more favorable at higher temperature.     

Unlocked disinfection by-product formation potential upon exposure of swimming pool water to additional stimulants

• Swimming pool water was studied for DBPs upon exposure to additional stimulants. • DBP formation could be induced by residual chlorine and extended incubation. • Urine led to a massive formation of chloroform with additional stimulants. • Reactions between chlorine and anthropogenic organics were slow and long-lasting. • Urine control and air ventilation should be on the priority list for pool management. Anthropogenic organics are known to be responsible for the formation of harmful disinfection by-products (DBPs) in swimming pool water (SPW). The research explored an important scenario of SPW with no additional anthropogenic organic input. With stimulations by residual chlorine or additional chlorine and extended incubation, the formation of DBPs, especially chloroform, was significantly induced. Similar observations were found by investigating synthetic SPW made with sweat and urine. The presence of urine led to a massive formation of chloroform, as noted by an approximate 19-fold increase after 165-day incubation with a shock chlorine dose. The research suggests that consistent residual chlorine and long water retention as two typical features of SPW could unlock the DBP formation potential of anthropogenic organics. Thus, limiting the introduction of anthropogenic organics may not have an immediate effect on reducing DBP levels, because their reactions with chlorine can be slow and long-lasting. Pool management should prioritize on control of urine and improving air ventilation. This work is useful to deepen understandings about DBP formation in SPW and provide implications for pool management and prospective legislation.     

Biological conversion pathways of sulfate reduction ammonium oxidation in anammox consortia

• The SRAO phenomena tended to occur only under certain conditions. • High amount of biomass and non-anaerobic condition is requirement for SRAO. • Anammox bacteria cannot oxidize ammonium with sulfate as electron acceptor. • AOB and AnAOB are mainly responsible for ammonium conversion. • Heterotrophic sulfate reduction mainly contributed to sulfate conversion. For over two decades, sulfate reduction with ammonium oxidation (SRAO) had been reported from laboratory experiments. SRAO was considered an autotrophic process mediated by anammox bacteria, in which ammonium as electron donor was oxidized by the electron acceptor sulfate. This process had been attributed to observed transformations of nitrogenous and sulfurous compounds in natural environments. Results obtained differed largely for the conversion mole ratios (ammonium/sulfate), and even the intermediate and final products of sulfate reduction. Thus, the hypothesis of biological conversion pathways of ammonium and sulfate in anammox consortia is implausible. In this study, continuous reactor experiments (with working volume of 3.8L) and batch tests were conducted under normal anaerobic (0.2≤DO<0.5 mg/L) / strict anaerobic (DO<0.2 mg/L) conditions with different biomass proportions to verify the SRAO phenomena and identify possible pathways behind substrate conversion. Key findings were that SRAO occurred only in cases of high amounts of inoculant biomass under normal anaerobic condition, while absent under strict anaerobic conditions for same anammox consortia. Mass balance and stoichiometry were checked based on experimental results and the thermodynamics proposed by previous studies were critically discussed. Thus anammox bacteria do not possess the ability to oxidize ammonium with sulfate as electron acceptor and the assumed SRAO could, in fact, be a combination of aerobic ammonium oxidation, anammox and heterotrophic sulfate reduction processes.