Removal Of Trace Organic Contaminants Research Articles

Flow Rate and Kinetics of Trace Organic Contaminants Removal in Black Carbon-Amended Engineered Media Filters for Improved Stormwater Runoff Treatment

Urban stormwater runoff is considered a key component of future water supply portfolios for water-stressed cities. Beneficial use of runoff, such as capture for recharge of drinking water aquifers, relies on improved stormwater treatment. Many dissolved constituents, including metals and trace organic contaminants (TrOCs) such as hydrophilic pesticides and poly- and perfluoroalkyl substances (PFASs), are of concern due to their toxicity, persistence, prevalence in stormwater runoff, and poor removal in conventional stormwater control measures. This study explores the operational flow rate limitations of black carbon (BC)-amended engineered media filters for removal of a wide suite of dissolved metals and TrOCs and provides validation for a previously developed predictive TrOC transport model. Column experiments were conducted with face velocities of 40 and 60 cm h−1 to assess Douglas Fir-based biochar and regenerated activated carbon (RAC) filter performance in light of media-contaminant removal kinetic limitations. This study found that increasing the face velocity in BC-amended filters to 40 and 60 cm h−1, which are representative of field conditions, decreased the removal of total suspended solids, turbidity, dissolved hydrophilic TrOCs, and PFASs when expressed as volume treated relative to previous studies conducted at 20 cm h−1. Dissolved metals and hydrophobic TrOCs removal were not substantially affected by the increased flow rates. A predictive 1-d intraparticle pore diffusion-limited sorption model with sorption and effective tortuosity parameters determined previously from experiments conducted at 20 cm h−1 was validated for these higher flow rates. This work provides insights to the kinetic limitations of contaminant removal within biochar and RAC filters and implications for stormwater filter design and operation.

Understanding Rejection Mechanisms of Trace Organic Contaminants by Polyamide Membranes via Data-Knowledge Codriven Machine Learning.

Data-driven machine learning (ML) provides a promising approach to understanding and predicting the rejection of trace organic contaminants (TrOCs) by polyamide (PA). However, various confounding variables, coupled with data scarcity, restrict the direct application of data-driven ML. In this study, we developed a data-knowledge codriven ML model via domain-knowledge embedding and explored its application in comprehending TrOC rejection by PA membranes. Domain-knowledge embedding enhanced both the predictive performance and the interpretability of the ML model. The contribution of key mechanisms, including size exclusion, charge effect, hydrophobic interaction, etc., that dominate the rejections of the three TrOC categories (neutral hydrophilic, neutral hydrophobic, and charged TrOCs) was quantified. Log D and molecular charge emerge as key factors contributing to the discernible variations in the rejection among the three TrOC categories. Furthermore, we quantitatively compared the TrOC rejection mechanisms between nanofiltration (NF) and reverse osmosis (RO) PA membranes. The charge effect and hydrophobic interactions possessed higher weights for NF to reject TrOCs, while the size exclusion in RO played a more important role. This study demonstrated the effectiveness of the data-knowledge codriven ML method in understanding TrOC rejection by PA membranes, providing a methodology to formulate a strategy for targeted TrOC removal.

Machine learning modeling of fluorescence spectral data for prediction of trace organic contaminant removal during UV/H2O2 treatment of wastewater

Dynamic feedback of the removal performance of trace organic contaminants (TrOCs) is essential towards economical advanced oxidation processes (AOPs), whereas the corresponding quick-response feedback methods have long been desired. Herein, machine learning (ML) multi-target regression random forest (MORF) models were developed based on the fluorescence spectra to predict the removal of TrOCs during UV/H2O2 treatment of municipal secondary effluent as a typical AOP. The predictive performance of the developed MORF model (R2 = 0.83-0.95) exhibited higher accuracy over the traditional linear regression models with R2 increased by ∼0.15. Furthermore, through feature importance analysis, the spectral regions of high importance were identified for different groups of TrOCs, thus enabling faster data acquisition due to remarkably reduced size of required fluorescence spectral scanning region. Specifically, the fluorescence regions Ex(235-275 nm)/Em(325-400 nm) and Ex(240-360 nm)/Em(325-450 nm) were found highly correlated with the removal of the TrOCs susceptible to both photodegradation and •OH degradation and those primarily subject to •OH degradation, respectively. In addition, the spectral regions of high importance were also individually identified for the investigated TrOCs during the AOP. Through providing an efficient ML-based feedback method to monitor TrOC removal during AOP, this study sheds light on the development of dynamic feedback-based strategies for precise and economical advanced treatment of wastewater.

Bioretention Design Modifications Increase the Simulated Capture of Hydrophobic and Hydrophilic Trace Organic Compounds.

Stormwater rapidly moves trace organic contaminants (TrOCs) from the built environment to the aquatic environment. Bioretention cells reduce loadings of some TrOCs, but they struggle with hydrophilic compounds. Herein, we assessed the potential to enhance TrOC removal via changes in bioretention system design by simulating the fate of seven high-priority stormwater TrOCs (e.g., PFOA, 6PPD-quinone, PAHs) with log KOC values between -1.5 and 6.74 in a bioretention cell. We evaluated eight design and management interventions for three illustrative use cases representing a highway, a residential area, and an airport. We suggest two metrics of performance: mass advected to the sewer network, which poses an acute risk to aquatic ecosystems, and total mass advected from the system, which poses a longer-term risk for persistent compounds. The optimized designs for each use case reduced effluent loadings of all but the most polar compound (PFOA) to <5% of influent mass. Our results suggest that having the largest possible system area allowed bioretention systems to provide benefits during larger events, which improved performance for all compounds. To improve performance for the most hydrophilic TrOCs, an amendment like biochar was necessary; field-scale research is needed to confirm this result. Our results showed that changing the design of bioretention systems can allow them to effectively capture TrOCs with a wide range of physicochemical properties, protecting human health and aquatic species from chemical impacts.

Elucidating the performance of UV-based photochemical processes for the removal of trace organic contaminants: Degradation and toxicity evaluation

In this study, the performance of standalone ultraviolet (UV) photolysis and UV-based advanced oxidation processes (AOPs), namely, UV/hydrogen peroxide, UV/chlorine, UV/persulphate, and UV/permonosulphate, were investigated for the degradation of 31 trace organic contaminants (TrOCs). Under the tested conditions, standalone UV photolysis did not achieve effective removal of TrOCs. To improve the degradation efficiency of UV photolysis, four different oxidants were added individually to the test solution. The effect of these oxidants in the absence of UV irradiation was also explored and only chlorine showed promising degradation of some contaminants. During the chlorination of 31 investigated TrOCs, only six demonstrated greater than 50% degradation. The combined UV-based AOPs demonstrated much improved degradation (ranging from 65 to 100%) depending on TrOC-structure and oxidant concentration. The UV/hydrogen peroxide process showed similar degradation of TrOCs, irrespective of the functional groups (i.e., electron withdrawing groups, EWGs and electron donating groups, EDGs) present in their structures. Conversely, the UV/sulphate and UV/chlorine based processes achieved better degradation of the TrOCs with EDGs in their structures. TrOCs degradation improved up to 40% when oxidants concentrations were increased from 0.1 to 1 mM, and further increasing the concentration to 2 mM did not improve degradation. Toxicity evaluation using bioluminescence test (BLT assay) demonstrated that except for UV/hydrogen peroxide, all UV-based AOPs increased the toxicity of the treated effluent, indicating generation of toxic by-products. This study elucidates the performance of four different UV-based AOPs for the removal of commonly detected diverse TrOCs for the first time.

Multi-Heteroatom Doped Fe@CN Activation Peroxomonosulfate for the Removal of Trace Organic Contaminants from Water: Optimizing Fabrication and Performance

Modification of catalysts by multi-heteroatom doping (S, P, B) is an effective way to improve the peroxomonosulfate activation performance of catalysts. In recent years, highly toxic and persistent trace organic contaminants have been frequently detected in water. Consequently, we proposed the advanced oxidation processes of peroxomonosulfate activated by multi-heteroatom doped Fe@CN (X-Fe@CN) to eliminate trace organic contaminants. The physical phases of X-Fe@CN and its precursors were characterized by X-ray diffraction and scanning electron microscopy. In evaluating the catalytic properties and iron ion leaching of X-Fe@CN-activated PMS for the removal of dicamba and atenolol, B-Fe@CN and PB-Fe@CN were selected and optimized. The active sites of the catalysts were characterized by X-ray photoelectron spectroscopy and Raman. The pathways of PMS activation by B-Fe@CN and PB-Fe@CN were identified in combination with electron paramagnetic resonance and electrochemical experiments. Defects, O-B-O and pyrrolic nitrogen on the surface of B-Fe@CN could adsorb and activate PMS to produce SO4•−, ·OH and 1O2. Further doping with P enhanced the electron transfer on the catalyst surface, thus accelerating the activation of peroxomonosulfate. This study compared the effects of multi-heteroatom modifications and further demonstrated the synergistic effect between P and B, which can provide a theoretical basis for the selection of multi-heteroatom doped catalysts in water treatment.

Colloid-bound radicals formed in NOM-enhanced Fe(III)/peroxymonosulfate process accelerate the degradation of trace organic contaminants in water

The omnipresence of natural organic matter (NOM) in water bodies traditionally hinders the degradation of trace organic contaminants (TrOCs) in peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs). This study elucidates the positive role of NOM in enhancing the degradation of TrOCs through the Fe(III)/PMS process. During this process, NOM reduces Fe(III), yielding semiquinone-like radical (NOM•) and concurrently forming NOM-Fe(III) colloids. In addition to the Fe(II)-mediated activation pathway, Fe(III) sites on NOM-Fe(III) colloids effectively transfer electrons from NOM• or some redox-active moieties to PMS, resulting in the generation of long-lived colloid-bound SO4•−, which can readily undergo hydrolysis to produce HO•. The stabilization of SO4•− and HO• by NOM-Fe(III) colloids, combined with their moderate adsorption of TrOCs, results in surface-confined reactions that significantly enhance TrOC removal, despite the presence of concurrent quenching reactions between radicals and NOM. Further, the significant positive correlation between the phenolic contents of eight NOM types and TrOC degradation kinetics suggests phenolic moieties as the primary electron source for PMS activation. By in-situ utilizing NOM in raw water, a PMS-amended iron coagulation process with 0.2 mM Fe(III) and PMS effectively removes 90–100 % of six coexisting TrOCs. This study unveils the previously unrecognized role of colloid-bound radicals in decontamination processes, offering valuable insights into harnessing NOM's influence in advanced oxidation water treatment processes.

Trace Organic Contaminant Removal from Municipal Wastewater by Styrenic β-Cyclodextrin Polymers.

Trace organic contaminants (TrOCs) present major removal challenges for wastewater treatment. TrOCs, such as perfluoroalkyl and polyfluoroalkyl substances (PFAS), are associated with chronic toxicity at ng L-1 exposure levels and should be removed from wastewater to enable safe reuse and release of treated effluents. Established adsorbents, such as granular activated carbon (GAC), exhibit variable TrOC removal and fouling by wastewater constituents. These shortcomings motivate the development of selective novel adsorbents that also maintain robust performance in wastewater. Cross-linked β-cyclodextrin (β-CD) polymers are promising adsorbents with demonstrated TrOC removal efficacy. Here, we report a simplified and potentially scalable synthesis of a porous polymer composed of styrene-linked β-CD and cationic ammonium groups. Batch adsorption experiments demonstrate that the polymer is a selective adsorbent exhibiting complete removal for six out of 13 contaminants with less adsorption inhibition than GAC in wastewater. The polymer also exhibits faster adsorption kinetics than GAC and ion exchange (IX) resin, higher adsorption affinity for PFAS than GAC, and is regenerable by solvent wash. Rapid small-scale column tests show that the polymer exhibits later breakthrough times compared to GAC and IX resin. These results demonstrate the potential for β-CD polymers to remediate TrOCs from complex water matrices.

Persistent Trace Organic Contaminants Are Transformed Rapidly under Sulfate- and Fe(III)-Reducing Conditions in a Nature-Based Subsurface Water Treatment System.

Subsurface treatment systems, such as constructed wetlands, riverbank filtration systems, and managed aquifer recharge systems, offer a low-cost means of removing trace organic contaminants from treated municipal wastewater. To assess the processes through which trace organic contaminants are removed in subsurface treatment systems, pharmaceuticals and several major metabolites were measured in porewater, sediment, and plants within a horizontal levee (i.e., a subsurface flow wetland that receives treated municipal wastewater). Concentrations of trace organic contaminants in each wetland compartment rapidly declined along the flow path. Mass balance calculations, analysis of transformation products, microcosm experiments, and one-dimensional transport modeling demonstrated that more than 60% of the contaminant removal could be attributed to transformation. Monitoring of the system with and without nitrate in the wetland inflow indicated that relatively biodegradable trace organic contaminants, such as acyclovir and metoprolol, were rapidly transformed under both operating conditions. Trace organic contaminants that are normally persistent in biological treatment systems (e.g., sulfamethoxazole and carbamazepine) were removed only when Fe(III)- and sulfate-reducing conditions were observed. Minor structural modifications to trace organic contaminants (e.g., hydroxylation) altered the pathways and extents of trace organic contaminant transformation under different redox conditions. These findings indicate that subsurface treatment systems can be designed to remove both labile and persistent trace organic contaminants via transformation if they are designed and operated in a manner that results in sulfate-and Fe(III)-reducing conditions.

Ultra-permeable polyamide nanofiltration membrane modified by hydrophilic-hydrophobic alternated lignocellulosic nanofibrils for efficient water reuse

Polyamide nanofiltration (NF) membranes are instrumental in water reuse due to their capability to efficiently remove trace organic contaminants (TrOCs), which pose potential health risks. However, while the current NF membranes offer acceptable TrOC rejection, their water permeance, which is highly related to the process energy consumption in water reuse, is relatively low. To address this limitation, we introduced a novel NF membrane by incorporating a lignocellulosic nanofibril interlayer—specifically, nanowires with alternating hydrophilic-hydrophobic regions (denoted as HONW). The resultant NF membrane achieved remarkable water permeance (52.4 L m−2 h−1 bar−1) while still ensuring high TrOC retention (including endocrine-disrupting compounds, pharmaceuticals, and antibiotics). A detailed mechanistic investigation revealed that the eliminated funnel effect or introduced gutter effect induced by the HONW interlayer, improved polyamide layer structure characterized by lower cross-linking degree and higher surface wettability, and reduced interlayer resistance (due to a unique water transport pattern: hydrophilic regions absorbed water molecules while hydrophobic regions strengthened water penetration) were significantly responsible for the enhanced membrane permeance. Moreover, the membrane also demonstrated low specific energy consumption as well as outstanding stability. This investigation unveils an appealing approach for constructing the ultra-permeable NF membrane for efficient water reuse.

Fe-loaded biochar thin-layer capping for the remediation of sediment polluted with nitrate and bisphenol A: Insight into interdomain microbial interactions

The information on the collaborative removal of nitrate and trace organic contaminants in the thin-layer capping system covered with Fe-loaded biochar (FeBC) is limited. The community changes of bacteria, archaea and fungi, and their co-occurrence patterns during the remediation processes are also unknown. In this study, the optimized biochar (BC) and FeBC were selected as the capping materials in a batch experiment for the remediation of overlying water and sediment polluted with nitrate and bisphenol A (BPA). The community structure and metabolic activities of bacteria, archaea and fungi were investigated. During the incubation (28 d), the nitrate in overlying water decreased from 29.6 to 11.0 mg L−1 in the FeBC group, 2.9 and 1.8 times higher than the removal efficiencies in Control and BC group. The nitrate in the sediment declined from 5.03 to 0.75 mg kg−1 in the FeBC group, 1.3 and 1.1 times higher than those in Control and BC group. The BPA content in the overlying water in BC group and FeBC group maintained below 0.4 mg L−1 during incubation, signally lower than in the Control group. After capping with FeBC, a series of species in bacteria, archaea and fungi could collaboratively contribute to the removal of nitrate and BPA. In the FeBC group, more metabolism pathways related to nitrogen metabolism (KO00910) and Bisphenol degradation (KO00363) were generated. The co-occurrence network analysis manifested a more intense interaction within bacteria communities than archaea and fungi. Proteobacteria, Firmicutes, Actinobacteria in bacteria, and Crenarchaeota in archaea are verified keystone species in co-occurrence network construction. The information demonstrated the improved pollutant attenuation by optimizing biochar properties, improving microbial diversity and upgrading microbial metabolic activities. Our results are of significance in providing theoretical guidance on the remediation of sediments polluted with nitrate and trace organic contaminants.

Thin film composite reverse osmosis membranes with metal-organic coordination complexes stabilized CNTs interlayer for enhanced removal of trace organic contaminants

Reverse osmosis (RO) has been recognized as a reliable technique for wastewater reclamation. To enhance its rejection of trace organic contaminants (TrOCs), a novel strategy was proposed to improve reverse osmosis (RO) membranes by fabricating thin-film nanocomposite membrane (TFNi) with a TA-Fe3+/CNTs interlayer. The TFNi-30 membrane was obtained by optimizing the loading capacity. This optimized membrane gave rise to an enhanced water permeance of 3.2 ± 0.2 L m-2 h-1 bar-1, which was two times higher than that of the control membrane (1.1 ± 0.2 L m-2 h-1 bar-1), while achieving a considerably higher rejection of inorganic salts and trace organic contaminants (TrOCs) thanks to the formation of a denser polyamide rejection layer. In addition, the specific roles of the interlayer structure in determining the separation performance of RO membranes were investigated by tailoring the support-free RO membranes and comparing them with the conventional membranes. This study would provide a peer reference for designing high performance RO membranes for wastewater reclamation via the TFNi strategy.

Chemodiversity transformation of organic matters in a full scale MBR-NF wastewater reclamation plant

Membrane bioreactor (MBR) and nanofiltration (NF) process has been attractive in wastewater reclamation, and was set as the target process in this study. Dissolved organic matter (DOM) and trace organic contaminants (TrOCs), closely associated with water safety, are noteworthy pollutants. Though the general DOM characteristics and TrOCs removal in MBR-NF reclamation process have been reported in lab‐/pilot-scale experiment, the molecular characteristics of DOM revealed by high resolution mass spectrometry, and the correlation between DOM and TrOCs have been rarely studied in full-scale MBR-NF wastewater reclamation plant. In this work, biological and NF processes contributed significantly to the removal of DOM and TrOCs, while MBR filtration contributed slightly. Spectroscopic analyses revealed that DOM with higher aromaticity and lower molecular weight were more recalcitrant along the treatment. Aromatic protein-like substances were preferentially removed comparing to humic-like substances. Fourier transform ion cyclotron resonance mass spectrometry was applied to investigate DOM transformation at molecular level. DOM molecules with higher H/C and lower O/C, especially the aliphatics and peptides, were readily biodegraded into higher‑oxygenate, highly unsaturated, and aromatic compounds. The generated species mainly included condensed aromatics, polyphenols, and highly unsaturated compounds. Filtration in MBR tended to reject higher oxygenated molecules. NF effectively removed most of the DOM molecules, especially higher oxygenated molecules with low H, N and S. The residual TrOCs in the NF effluent, including sulfamethoxazole, ofloxacin, and bisphenol A, still displayed above medium environmental risk. Significant correlations were found among organic compounds, spectral indices, and peptides molecules. Positive correlation between most of the TrOCs and several DOM parameters implied that they were synchronously removed in biological and membrane filtration processes. SUVA and FI might be potential indexes in monitoring the performance of MBR-NF process in both DOM and TrOC removal. These findings would expand the understanding of DOM and TrOCs behavior in wastewater reclamation process and simplify an in-depth system monitoring.

Waste leather derived porous carbon boosted Fenton oxidation towards removal of diethyl phthalate: Mechanism and long-lasting performance

The acceleration of Fe(III)/Fe(II) conversion in Fenton systems is the critical route to achieve the long-lasting generation of reactive oxygen species towards the oxidation of refractory contaminants. Here, we found that waste leather derived porous carbon materials (LPC), as a simple and readily available metal-free biochar material, can promote the Fe(III)/H2O2 system to generate hydroxyl radicals (•OH) for oxidizing a broad spectrum of contaminants. Results of characterizations, theoretical calculations, and electrochemical tests show that the surface carbonyl groups of LPC can provide electron for direct Fe(III) reduction. More importantly, the graphitic-N on surface of LPC can enhance the reactivity of Fe(III) for accelerating H2O2 induced Fe(III) reduction. The presence of LPC accelerates the Fe(III)/Fe(II) redox cycle in the Fe(III)/H2O2 system, sustainable Fenton chain reactions is thus initiated for long-lasting generation of hydroxyl radicals without adding Fe(II). The continuous flow mode that couples in-situ Fenton-like oxidation and LPC with excellent adsorption catalytic properties, anti-coexisting substances interference and reusability performance enables efficient, green and sustainable degradation of trace organic pollutants. Therefore, the application of metal-free carbon materials in Fenton-like system can solve its rate-limiting problem, reduce the production of iron sludge, achieve green Fenton chemistry, and facilitate the actual engineering application of economic and ecological methods to efficiently remove trace organic contaminants from actual water sources.

Genipin and glutaraldehyde based laccase two-layers immobilization with improved properties: New biocatalysts with high potential for enzymatic removal of trace organic contaminants

This research proposes the preparation of a two-layer laccase biocatalyst using genipin or/and glutaraldehyde as cross-linking agents. The multilayer biocatalysts were prepared using different combinations of genipin and glutaraldehyde in the individual preparation of the first and second laccase layers. First, chitosan was treated with genipin or glutaraldehyde, followed by the immobilization of the first laccase layer to form a single-layer biocatalyst. Then, the immobilized laccases were coated once again with genipin or glutaraldehyde, and a new laccase layer was immobilized onto the system, resulting in the final two-layer biocatalyst. Compared to the single-layer biocatalysts, catalytic activity increased 1.7- and 3.4-fold when glutaraldehyde coating was used to prepare the second laccase layer. However, adding a second layer did not always produce more active biocatalysts, since the two-layer biocatalysts prepared with genipin (GenLacGenLac and GluLacGenLac) presented a decrease in activity of 65% and 28%, respectively. However, these two-layer biocatalysts prepared with genipin maintained 100% of their initial activity after 5 cycles of ABTS oxidation. Nevertheless, the two-layer, genipin-coated biocatalyst resulted in a higher removal of trace organic contaminants, since it removed 100% of mefenamic acid and 66% of acetaminophen, compared with the glutaraldehyde-coated biocatalyst, which removed 20% of mefenamic acid, and 18% of acetaminophen.

Methane-Oxidizing Activity Enhances Sulfamethoxazole Biotransformation in a Benthic Constructed Wetland Biomat.

Ammonia monooxygenase and analogous oxygenase enzymes contribute to pharmaceutical biotransformation in activated sludge. In this study, we hypothesized that methane monooxygenase can enhance pharmaceutical biotransformation within the benthic, diffuse periphytic sediments (i.e., "biomat") of a shallow, open-water constructed wetland. To test this hypothesis, we combined field-scale metatranscriptomics, porewater geochemistry, and methane gas fluxes to inform microcosms targeting methane monooxygenase activity and its potential role in pharmaceutical biotransformation. In the field, sulfamethoxazole concentrations decreased within surficial biomat layers where genes encoding for the particulate methane monooxygenase (pMMO) were transcribed by a novel methanotroph classified as Methylotetracoccus. Inhibition microcosms provided independent confirmation that methane oxidation was mediated by the pMMO. In these same incubations, sulfamethoxazole biotransformation was stimulated proportional to aerobic methane-oxidizing activity and exhibited negligible removal in the absence of methane, in the presence of methane and pMMO inhibitors, and under anoxia. Nitrate reduction was similarly enhanced under aerobic methane-oxidizing conditions with rates several times faster than for canonical denitrification. Collectively, our results provide convergent in situ and laboratory evidence that methane-oxidizing activity can enhance sulfamethoxazole biotransformation, with possible implications for the combined removal of nitrogen and trace organic contaminants in wetland sediments.

Cost-effective, scalable production of glucose oxidase using Casuarina equisetifolia biomass and its application in the bio-Fenton oxidation process for the removal of trace organic contaminants from wastewater

This study focuses on using Casuarina equisetifolia biomass for pilot-scale glucose oxidase production from Aspergillus niger and its application in the removal of trace organic contaminants (TrOCs) from municipal wastewater through the bio-Fenton oxidation. The cost of glucose oxidase was 0.005 $/U, including the optimum production parameters, 10% biomass, 7% sucrose, 1% peptone, and 3% CaCO3 at 96 h with an enzyme activity of 670 U/mL. Optimized conditions for H2O2 were 1 M glucose, 100 U/mL glucose oxidase, and 120 mins of incubation, resulting in 544.3 mg/L H2O2. Thus, H2O2 produced under these conditions lead to bio-Fenton oxidation resulting in the removal of 36–92% of nine TrOCs in municipal wastewater at pH 7.0 in 360 mins. Therefore, this work establishes the cost-effective glucose oxidase-producing H2O2 as an attractive bioremediating agent to enhance the removal of TrOCs in wastewater at neutral pH.

Tailoring the draw solution chemistry in the integrated electro-Fenton and forward osmosis for enhancing emerging contaminants removal: Performance, DFT calculation and degradation pathway

Integrated electro-Fenton and forward osmosis is capable to simultaneously separate emerging contaminants and degrade accumulated ones. Thus, an understanding of how draw solution chemistry in forward osmosis influences electro-Fenton is vital for maximizing overall treatment. Therefore, this study aimed to determine the transport behavior of four trace organic contaminants (TrOCs) including Diuron, Atrazine, DEET and Sulfamethoxazole under several influencing factors. Alkalic NaCl severely deteriorated degradation because of the less generation of OH caused by the interfered iron redox cycle. pH-neutral NaCl resulted in the highest reverse salt flux, namely possible largest production of active chlorine, therefore leading to the highest degradation. Compared to NaCl, Na2SO4 presented a significant lower reverse diffusion due to the larger hydrated radius of SO42- than Cl-. Meanwhile, the large consumption of OH by SO42- decreased degradation. Dissolved organic matters in the secondary effluent acted as the scavenger for OH and resulted in a degradation decline. Water extraction resulted from forward osmosis deteriorated degradation kinetics of all compounds except Sulfamethoxazole. On the other hand, Density functional theory calculations and identified intermediates contributed to propose the possible degradation pathways for each TrOC in terms of understanding TrOCs removal mechanism.

Molecular Design of the Polyamide Layer Structure of Nanofiltration Membranes by Sacrificing Hydrolyzable Groups toward Enhanced Separation Performance.

Nanofiltration (NF) is an effective technology for removing trace organic contaminants (TrOCs), while the inherent trade-off effect between water permeance and solute rejections hinders its widespread application in water treatment. Herein, we propose a novel scheme of "monomers with sacrificial groups" to regulate the microstructure of the polyamide active layer via introducing a hydrolyzable ester group onto piperazine to control the diffusion and interfacial polymerization process. The achieved benefits include narrowing the pore size, improving the interpore connectivity, enhancing the microporosity, and reducing the active layer thickness, which collectively realized the simultaneous improvement of water permeance and enhancement of TrOCs rejection performance. The resulting membranes were superior to both the control and commercial membranes, especially in water-TrOCs selectivity. The effects of using the new monomers on the membrane physicochemical properties were systematically studied, and underlying mechanisms for the enhanced separation performance were further revealed by simulating the polymerization process through density functional theory calculation and measuring the trans-interface diffusion rate of monomers. This study demonstrates a novel promising NF membrane synthesis strategy by designing the structure of reaction monomers for achieving excellent rejection of TrOCs with a low energy input in water treatment.

Enhancing Stability of Tannic Acid-FeIII Nanofiltration Membrane for Water Treatment: Intercoordination by Metal-Organic Framework.

Tannic acid (TA)-FeIII nanofiltration (NF) membrane has been demonstrated to possess more favorable removal of trace organic contaminants (TrOCs) over the conventional polyamide NF membrane. However, the drawback of acid instability severely hinders the practical application of TA-FeIII NF membrane in the treatment of (weak) acidic wastewater containing TrOCs (e.g., pharmaceutical wastewater, surface water, and drinking water). Herein, we introduced the MIL-101(Cr) nanoparticle, a kind of metal-organic framework (MOF), into the TA-FeIII selective layer to enhance the membrane acid stability. The acid-tolerance parameter of MIL-101(Cr)-stabilized TA-FeIII membrane (TA-FeIII-MOF membrane, 12,000 ppm/s-1) was two orders of magnitude larger than that of the TA-FeIII membrane (50 ppm/s-1), and the TA-FeIII-MOF membrane can withstand acid treatment at pH = 4 for more than 30 days. Meanwhile, the TA-FeIII-MOF membrane displayed increased water permeance from 9.5 to 12.7 L/(m2·h·bar) after the MOF addition, without compromising the selectivity. The enhanced acid stability for the TA-FeIII-MOF membrane was ascribed to an intercoordination mechanism, where FeIII centers (from TA-FeIII complex) coordinated with -COOH groups (from terephthalic acid of MOF) and CrIII centers (from MOF) coordinated with -OH groups (from TA of TA-FeIII complex), which was verified by the density functional theory calculation. This study highlights a new approach for the development of a TA-FeIII-based NF membrane with markedly enhanced acid stability, which is important for its real application in wastewater treatment and water reuse.