Removal Of Organic Micropollutants Research Articles

The first and cost-effective nano-biocomposite ZnPor/rGO/TiO2 as efficient UV photocatalysts for ethylparaben decomposition

Organic micropollutants are considered as dangerous wastes to aquatic environments, which threaten the life of living beings. The efficacious removal of these pollutants from surrounding aquatic ecosystems has been taken into consideration in water refinery technologies. In this study, a bio-nanocomposite was developed through a green approach involving self-assembly of reduced graphene oxide (rGO) with zinc [5,10,15,20-tetrakis(2,6-dichlorophenyl) porphyrin] complex (ZnPor) and TiO2 nanoparticles using reflux method. This organic/inorganic hybrid material was characterized using FE-SEM, XRD, EIS, RAMAN, and UV–Vis spectroscopy. The band-gap energies were found to range from 3.32 eV for GO to 2.35 eV for ZnPor/rGO/TiO2, indicating the composites behave as semiconductor materials. The photocatalytic activity was highest for the ZnPor/rGO/TiO2 composite based on 200 mL ZnPor addition during the synthesis process, achieving 98.1 % degradation of the model pollutant ethylparaben after only 20 min of UV treatment. The rGO facilitates electron-hole separation and transportation, while the ZnPor broadens the light absorption range and improves charge transfer. The TiO2 nanoparticles provide the primary photocatalytic sites. These synergistic effects enhanced the photocatalytic activity of the ZnPor/rGO/TiO2 system. This green-synthesized, eco-friendly, and highly efficient photocatalyst shows great promise for the removal of organic micropollutants from wastewater.

Removal of Organic Micropollutants and Microplastics via Ozonation Followed by Granular Activated Carbon Filtration

Discharge from Wastewater Treatment Plants (WWTPs) can result in the emission of organic micropollutants (OMPs) and microplastics (MPs) into the aquatic environment. To prevent this harmful release, a pilot plant consisting of an ozonation followed by a granular activated carbon (GAC) filter was operated at a WWTP in Germany, and its side-effects on the concentrations of nitrogen (N) and phosphorous (P) compounds were measured. Over 80% of OMPs and transformation products were removed during the operating time (around 6000 bed volumes) no matter the ozone dose (from around 0.1 to 0.5 mgO3/mgDOC), except for Diatrizoic acid, whose breakthrough appeared at 3500 BV. Formation of the oxidation by-product, NDMA, increased with higher ozone doses, but the concentration remained below 100 ng/L. Bromate was formed at a higher ozone dose (>0.4 mgO3/mgDOC) but at a low concentration—below 10 µg/L. The MP particles detected in the inflow (PE, SBR, PP, and PS) were effectively eliminated to a high degree, with a removal rate of at least 92%. Carbon parameters (COD, DOC, and SAC254) were removed further by the pilot plant, but to different extents. As expected, nitrate was formed during ozonation, while nitrite’s concentration decreased. Further, nitrite decreased and nitrate increased within the GAC filter, while ammonium was eliminated by at least 90%. Total P concentration decreased after the pilot, but the concentration of PO4-P increased.

Biodegradation of organic micropollutants by anoxic denitrification: Roles of extracellular polymeric substance adsorption, enzyme catalysis, and reactive oxygen species oxidation

The control of organic micropollutants (OMPs) in water environments have received significant attention. Denitrification was reported to exhibit good efficiency to remove OMPs, and the mechanisms involved in are too intricate to be well illustrated. In this study, we selected nitrobenzene [NB] and bisphenol A [BPA] as model pollutants and aimed to unravel the mechanisms of Paracoccus Denitrificans in the removal of OMPs, with a specific emphasis on aerobic behavior during denitrification processes. We demonstrated the formation of extracellular superoxide radicals, i.e., extracellular •O2-, using a chemiluminescence probe and found that extracellular polymeric substance adsorption, extracellular •O2-, and microbial assimilation contributed approximately 40 %, 10 %, and 50 % to OMPs removal, respectively. Transcriptome analysis further revealed the high expression and enrichment of several pathways, such as drug metabolism-other enzymes, of which a typical aerobic enzyme of polyphenol oxidase [PPO] participates in the degradation of NB and BPA. Importantly, all the immediate products showed a significant decrease in toxicity during the aerobic activity-related OMPs degradation process based on the proposed degradation pathways. This study demonstrates the formation of extracellular •O2- and the mechanisms of extracellular •O2-- and PPO-mediated OMPs biodegradation, and offers new insights into OMPs control in widely-used denitrification treatment processes.

A machine learning based framework to tailor properties of nanofiltration and reverse osmosis membranes for targeted removal of organic micropollutants

Nanofiltration (NF) and reverse osmosis (RO) membranes play an increasingly important role in the removal of organic micropollutants (OMPs), which puts higher demands on the customization of membranes suitable for OMPs removal based on the rejection mechanisms. Here, the pathways of OMPs-targeted optimization for membranes were constructed by using machine learning (ML) to capture the correlations between OMPs removal efficiency with properties of membranes and OMPs. Through expertise assistance and rigorous modeling methodology, an accurate and robust Extreme Gradient Boosting (XGBoost) model was established, which could well recognize the dominant rejection mechanisms of OMPs (i.e., the size exclusion effect and electrostatic interactions). An exemplary application to another dataset of several high-risk OMPs showed how the optimized model could be used to estimate the overall efficiency of OMPs risk control and, more importantly, to provide quantitative guidance on membrane properties for specific removal targets. The satisfying prediction results demonstrated the good generalization of the ML model and consequently its ability to sensitively define the ideal membrane properties for the targeted removal of these (and any other concerned) OMPs. This study provides a feasible and universal ML-based framework to achieve the tailored selection and design of NF/RO membranes for OMPs risk control.

Porous calix[4]pyrrole-based polymers with high surface area for efficient removal of polar organic micropollutants from water

Herein, effort was made to construct innovative adsorbent for the removal of polar organic micropollutants (OMPs) from water. Tetra-meso resorcinol-functionalized calix[4]pyrrole (CP) featured with endo-functionalized attribute and polyphenol hydroxyl structure was crosslinked by π-electron-rich 4,4′-bis(chloromethyl)biphenyl (BCMBP) through Friedel-Crafts reaction to generate porous calix[4]pyrrole-based polymers (PCPPs) with high surface area. The porosity of the PCPPs could be tuned by adjusting the molar ratio of hydrophilic CP to hydrophobic BCMBP, and diversified binding sites were integrated together. Based on adsorption kinetics and isotherm studies, PCPP(1–16) showed rapid adsorption rate and high removal efficiency (RE) as well as advanced adsorption capacity. The REs towards the tested polar OMPs by PCPP(1–16) were all above 95% in 30 min. Compared with granular activated carbon (GAC), the rate constant of pseudo-second-order model (k2) and adsorption capacity upon PCPP(1–16) were 8–230 times and 1.3–3.1 times greater than those by GAC. Adsorption mechanism studies confirmed the presence of multiple interactions and thermodynamic investigation revealed the spontaneous and physical adsorption nature. Besides, PCPP(1–16) showed excellent adsorption performance in real water samples at environmental levels and exhibited advanced absorption ability in flow-through mode. Accompanied by facile regeneration under eluting with methanol and cost-effective preparation, PCPP(1–16) demonstrated great potential as promising adsorbent for water treatment.

Peracetic acid activation by chitosan-derived nitrogen-doped carbon spheres loaded with zero-valent copper for efficient sulfamethazine degradation in groundwater

Herein, chitosan-derived nitrogen-doped carbon spheres supported zero-valent copper (Cu@NCs) was prepared for the activation of peracetic acid (PAA) to degrade sulfamethazine (SMT) in groundwater under neutral condition. Several key influencing factors such as pyrolysis temperature, PAA concentration, Cu@NCs dosage, initial pH, inorganic ions and humic acid (HA) were investigated. The findings displayed that the Cu@NCs/PAA system could effectively degrade 94.5 % SMT (10.0 μM) in simulated groundwater in 30 min at low concentrations of PAA (50.0 μM), and the optimum pH was 7. Radical quenching experiments and EPR examinations verified that radicals (•OH, R-O• and O2•−) and non-radical 1O2 were produced in the Cu@NCs/PAA system, with R-O• and 1O2 being the primary contributors to the elimination of SMT. Zero-valent copper continuously transfers electrons through carbon spheres (electron shuttles) to produce Cu+, effectively activating the PAA to produce the active substance, accompanied by the production of Cu2+. Subsequently, Cu0 could convert the produced Cu2+ to Cu+ and then participate in the activation of the PAA. Direct electron transfer from SMT to PAA was enhanced by catalyst-mediated processes, which benefited from the function of carbon spheres in electron transport. Through cooperative efforts across radical and non-radical pathways, SMT was rapidly removed with trace amounts of PAA. In addition, inorganic ions (Cl−, SO42−, and HCO3−) had almost no effect on the Cu@NCs/PAA system, while HA had a certain degree of inhibition on the degradation of SMT. Furthermore, the Cu@NCs/PAA system displayed good reusability and easy recyclability. This work offered fresh perspectives and ideas on the removal of organic micropollutants using copper-based materials in the field of PAA-based AOPs, which promises to be an antibiotic-contaminated groundwater remediation solution.

Removal of persistent and mobile organic micropollutants from drinking water utilizing a synthesized waste-derived adsorbent

Persistent and mobile (PM) substances refer to a wide range of organic micropollutants (OMPs) with high persistence and mobility in water. So far, only a few methods have been explored for the removal of PM substances from drinking water. In this work, a new adsorbent based on spent coffee grounds and aluminum waste was synthesized and utilized to remove 25 OMPs, including 22 PM substances, from drinking water. Different characterization methods, including powder X-ray diffraction (XRD), analyses according to Brunauer−Emmett−Teller (BET), field-emission scanning electron microscopy (FE-SEM) and energy dispersive X-ray spectroscopy (EDS), were applied to describe the adsorbent's textural and structural characteristics. The results revealed that the adsorbent is highly effective in removing OMPs. Common OMPs (i.e. carbamazepine, sulfamethoxazole and diclofenac) were completely removed from drinking water. Also, many of the PM substances were removed by more than 80% using an adsorbent dosage of 0.1 g/L. A strong relation between abatement of ultraviolet light absorbance at 254 nm (UV254) and OMP removal was observed. Therefore, UV254 abatement is a useful surrogate for a quick estimation of OMP removals.

Sludge size affects sorption of organic micropollutants in full-scale aerobic granular sludge systems

Aerobic granular sludge (AGS) is gaining popularity as an alternative to activated sludge for wastewater treatment. However, little information is available on AGS regarding the removal of organic micropollutants (OMPs) through sorption. In this study, the sorption behavior of 24 OMPs at environmentally relevant concentrations (1 μg/L) was investigated in six sludge fractions of varying sizes (>4 mm, 2–4 mm, 1–2 mm, 0.6–1 mm, 0.2–0.6 mm, and <0.2 mm) from a full-scale AGS reactor using batch experiments. Sorption was significant (removal efficiency >40 %) for 10 OMPs, including 4 zwitterionic and 6 positively charged pharmaceuticals, indicating the importance of electrostatic interaction for OMP sorption in AGS systems. Larger granules exhibited a higher sorption coefficient and capacity than smaller AGS fractions, probably due to increased extracellular polymeric substance content for larger granules. Equilibrium OMP sorption was only reached after 72 h in granules larger than 2 mm, indicating an effect of longer diffusion distance for OMPs into larger granules. Additionally, compared to activated sludge, AGS demonstrates a similar or even slightly higher sorption capacity for 10 OMPs at 1 μg/L. Overall, this study is the first to investigate the sorption behavior of six AGS size fractions for OMPs at environmentally relevant concentrations (1 μg/L) and propose the possible roles of different-sized sludge in OMP sorption in the full-scale AGS reactor.

Mastering granular activated carbon filtration to remove organic micropollutants, antibiotic resistance and metals for municipal wastewater reuse

GAC filtration of municipal wastewater was optimized and intensified, making its implementation and operation directly after secondary clarification possible and relevant. GAC was first selected based on laboratory tests. Performances on organic micropollutants were linked to the repartition of BET surface between micropores and meso/macropores. At pilot scale, in order to limit the impact of head loss, downflow declogging sequences (DCS) were implemented and upflow filtration tested. 6 to 12 DCS per day led to a 4.7–5.5-fold increase of particles retention capacity between backwashes (cycle duration of 20–120 h), and upflow operations improved head loss evolution profile with only a slight GAC (<15 %) expansion. DCS allows backwash frequency reduction, enabling significant water savings. Both adaptations maintained high organic micropollutants removals compared to a review of 16 GAC studies at pilot or full-scale, results being in the upper range. A specific dose of 2.0–2.5 g GAC/gC was necessary to obtain an average removal of pharmaceuticals and benzotriazole of 80 % at 20 min contact time, which is comparable to PAC and low granulometry GAC. Higher doses are needed for PFAS but >80 % removals are achievable. Particles, TKN, particulate phosphorus and organic matter are well removed by GAC filtration in both configurations. Biological activity is observed through nitrogen transformation in the GAC bed. Heavy metals are greatly removed in GAC filtration, in particular Cd, Cu, Ni and Pb, probably through biosorption onto the biofilm, developed within the GAC bed. For wastewater reuse applications, GAC filtration has an added value through physicochemical quality improvement and fecal contamination indicators removal of 1 log, facilitating the implementation and optimizing the design of a post-disinfection. Antibiotic resistant bacteria and antibiotic resistance genes are also partially retained in GAC filtration. Finally, biological wastewater treatments combined to GAC filtration is a good solution to effectively treat organic micropollutants together with heavy metals and preparing post-disinfection for reuse.

Application of high-dose UV irradiation as nanofiltration pretreatment for drinking water production: Organic fouling mitigation and micropollutant removal

Nanofiltration (NF) is being increasingly applied to produce high-quality drinking water; however, its cost-effective operation remains challenging due to the perennial membrane fouling. On account of the low tolerance of common NF membranes to chemical oxidants, this study proposed high-dose UV irradiation as a pretreatment strategy for organic fouling mitigation. Results showed that the permeate flux decline of the membrane with UV-treated feedwater (with a dose of 750 mJ cm−2) was less drastic than that with raw feedwater, but slightly faster as compared to that with UV/Cl2 pretreatment. The final normalized fluxes were 0.69, 0.79, and 0.82, respectively, after 10 h of operation with raw, UV- and UV/Cl2-treated feedwaters. With the characterization of feedwaters and membranes, the fouling was found to be initiated by the adsorption of hydrophilic biopolymers onto the membrane, followed by the deposition of hydrophobic humic substances. Reduction of the “glue” biopolymers was crucial to membrane fouling mitigation. The applicability of UV pretreatment in practice was testified with a pilot-scale UV-NF system where permeate flux of the NF module decreased by 37% after six-week continuous operation. Moreover, UV pretreatment could remove most of the identified pesticides in the feedwater with a removal efficiency over 80% for metolachlor and imidacloprid, but had no or even a negative effect on perfluorinated compounds. This work discloses the efficacy and mechanism of high-dose UV irradiation for NF membrane fouling control, which facilitates future research and application of NF technology.

Economical and rapid mechanochemical synthesis of porous organic adsorbents with high hydrophilicity for ultra-fast removal of organic micro-pollutants from water

Various porous adsorbent materials have shown excellent adsorption performance for the removal of organic micro-pollutants in water. However, the practical application was hindered by the high cost or slow adsorption kinetics for most of porous adsorbents. Therefore, it is of great significance to develop economic adsorbent materials with characteristic like low-cost, easier preparation method, excellent adsorption kinetics etc.Herein, based on the Friedel-Crafts alkylation reaction, we reported three novel hydrophilic organic porous adsorbent frameworks (PAF-210, PAF-211 and PAF-212) with high Brunauer-Emmet-Teller (BET) surface area (956 ∼ 1384 m2/g) for phenolic micro-pollutants (bisphenol A (BPA), 2,4-dichlorophenol (2,4-DCP) and 2-naphthol (2-NO)) adsorption in water, which were prepared by using cheap trimethyl orthoformate (TMOF) as crosslinker and one-step simple ball milling synthetic method under room temperature within 15 min. Rich oxygen content promotes the resulting polymers to possess excellent hydrophilicity and wettability through water vapor adsorption and water contact angle analysis. The excellent hydrophilicity and proper porous properties made the resulting frameworks suitable as porous organic adsorbents to rapidly remove organic phenolic micro-pollutants from water. Among the resulting polymers, the PAF-210 exhibited ultra-fast adsorption (>94.0 % within 5 s), ultra-rapid adsorption kinetics with pseudo-second-order rate constants (K2, up to 7.72g/mg min−1 for 2,4-DCP), high pollutant adsorption capacity (up to 867.03 mg g−1 for BPA) and excellent recyclability (10 cycles with slight loss in adsorption capacity) through systematically characterization. The adsorption performances of PAF-210 are much better than these of the commercial activated carbons and β-cyclodextrin-based porous adsorbents (K2 = 1.50g/mg min−1 for P-CDP) etc. The favorable hydrophilicity, surface wettability, and adsorption performance of PAF-210 were significantly better than the comparative material constructed by using benzene and formaldehyde dimethyl acetal (FDA) through conventional thermal synthetic method, which is a very classic synthesis strategy in the field of porous materials. More importantly, the PAF-210 exhibited relatively superior adsorption performance on BPA, and it still presented excellent adsorption performance (removal efficiency ≥ 96.8 % within 5 s after 10 cycles) even at the safe range of BPA quantified in drinking water (BPA≤10 μg L−1, Standards for drinking water quality, GB5749-2022, China). XPS analysis and theoretical simulations proved that the excellent adsorption performance and ultra-fast adsorption rate stem from interactions including π-π interactions, hydrogen bonding and van der Waals interactions between PAF-210 and micro-pollutants.

Adsorption of organic micropollutants in water: A review of advances in modelling, mechanisms, adsorbents, and their characteristics

The presence of organic micropollutants (OMPs) in water resources poses significant environmental and health risks due to their bioaccumulative and toxic properties. Adsorption technologies offer a promising solution for removing OMPs from water, yet comprehensive information on their development and application is limited. This review examines recent advancements in OMP removal using adsorption technologies, focusing on isotherms, breakthroughs, and kinetics modelling in both batch and column adsorption systems. It explores the mechanisms and characteristics of various adsorbents, highlighting significant progress in synthesizing green, mineral, porous carbon, and nanomaterial adsorbents. These developments aim to enhance properties like surface area, pore structure, surface chemistry, and particle size to optimize OMP adsorption. Despite the existence of accurate models for OMP removal by porous carbons, there is a gap in models for other adsorbents and a research bias toward batch systems. This review underscores the need for more research, particularly in computational simulation, to develop and optimize suitable models for predicting the removal of different OMPs from water via adsorption technologies using novel adsorbents in continuous column adsorption systems, to enhance the practical application of adsorption technologies in drinking water purification.

Comparing the performance of microbial electrochemical assisted and aerated treatment wetlands in pilot-scale: Removal of major pollutants and organic micropollutants

The combination of treatment wetlands (TWs) with microbial electrochemical technologies (MET) is often studied in the lab to improve the performance and decrease the footprint of TWs. In this article we evaluated the long-term performance of four pilot-scale vertical sub-surface flow TWs for major pollutants' and organic micropollutants' removal from domestic wastewater. Three of them were filled with electroconductive material and operated under saturated (MET SAT), unsaturated (MET UNSAT) and unsaturated-saturated (MET HYBRID) conditions while the fourth one was a saturated intensified aerated system (AEW) filled with gravel. The MET-TWs achieved significant removals of COD (>78 %) with no clogging issues at the maximum applied OLR (249 g COD m−3 d−1) while under these loading conditions TSS removal exceeded 84 %. Among all electroactive TWs, UNSAT could remove 25 g NH4-N m−3 d−1 through nitrification when peak ammonium loading rate was applied; however this removal was significantly lower than AEW (35 g NH4-N m−3d−1). No important removal of P was observed in all systems with the exception of MET-SAT were precipitation reactions of P with iron occurred when anaerobic pretreated wastewater was used. The removal of the sum of studied organic micropollutants ranged between 70 ± 18 % (MET UNSAT) to 91 ± 4 % (AEW) and improved with feeding pulses increase. Moderate to high removal of specific microcontaminants was observed depending on the target compound, the studied system and the operational conditions. AEW and MET HYBRID systems complied with the limits set by EU for wastewater discharge to non-sensitive water bodies and for Class B water reuse. Scale-up calculations for a settlement of 500 PE showed that these systems require much less area per PE (0.51 m2 PE−1) comparing to conventional TWs while the operational cost was calculated to 0.07 € m−3 for the AEW and 0.02 € m−3 for the MET HYBRID.

Adsorptive-Photocatalytic Composites of α-Ferrous Oxalate Supported on Activated Carbon for the Removal of Phenol under Visible Irradiation.

Adsorptive-photocatalytic composites based on activated carbon (AC) and α-ferrous oxalate dihydrate (α-FOD) were synthesized by an original two-step method and subsequently used for the removal of phenol from aqueous solutions. To obtain the composites, ferrotitaniferous black mineral sands (0.6FeTiO3·0.4Fe2O3) were first dissolved in an oxalic acid solution at ambient pressure, and further treated under hydrothermal conditions to precipitate α-FOD on the AC surface. The ratio of oxalic acid to the mineral sand precursor was tuned to obtain composites with 8.3 and 42.7 wt.% of α-FOD on the AC surface. These materials were characterized by X-ray powder diffraction, scanning electron microscopy, and the nitrogen adsorption-desorption method. The phenol removal efficiency of the composites was determined during 24 h of adsorption under dark conditions, followed by 24 h of adsorption-photocatalysis under visible light irradiation. AC/α-FOD composites with 8.3 and 42.7 wt.% of α-FOD adsorbed 60% and 51% of phenol in 24 h and reached a 90% and 96% removal efficiency after 12 h of irradiation, respectively. Given its higher photocatalytic response, the 42.7 wt.% α-FOD composite was also tested during successive cycles of adsorption and adsorption-photocatalysis. This composite exhibited a reasonable level of cyclability (~99% removal after four alternated dark/irradiated cycles of 24 h and ~68% removal after three simultaneous adsorption-photocatalysis cycles of 24 h). The promising performance of the as-prepared composites opens several opportunities for their application in the effective removal of organic micropollutants from water.

Feasibility of organic micropollutant removal from municipal wastewaters by algal treatment vs. activated sludge treatment: Comparison based on non-targeted organic compound analysis

Sustainability and life-cycle concerns about the conventional activated sludge (CAS) process for wastewater treatment have been driving the development of energy-efficient, greener alternatives. Feasibility of an algal-based wastewater treatment (A-WWT) system has been demonstrated recently as a possible alternative, capable of simultaneous nutrient and energy recovery. This study compared capabilities of the A-WWT and CAS systems in removing organic micropollutants (OMP). Initial assessments based on surrogate organic measures and fluorescence excitation-emission matrix (FEEM) scans revealed that the A-WWT system achieved higher removals of organics than the CAS system. However, effluents of both systems contained residual organic matter, necessitating further OMP assessment for a rigorous comparison. A novel ultrahigh-performance liquid chromatography- Fourier transform mass spectrometry (UPLC-FTMS)-based non-targeted screening approach was adopted here for residual OMP analysis. This approach confirmed that the A-WWT system resulted in better OMP removal, eliminating 329 compounds and partially reducing 472 compounds, compared to 206 eliminations and 410 partial reductions by the CAS system. Mass spectra signal corresponding to some OMPs increased with treatment while some transformation products were observed following treatment. Higher OMP reduction in the A-WWT system with concurrent reductions of biodegradable carbon, nutrients, and pathogens in a single-step while producing energy and nutrient rich algal biomass underscore its potential as a greener alternative for wastewater treatment.

Distinct Efficacies of Interlayers in Tailoring Polyamide Nanofiltration Membrane Performance for Organic Micropollutant Removal: Dependent on Substrate Characteristics.

Interlayered thin-film nanocomposite (TFN) membranes have shown the potential to boost nanofiltration performance for water treatment applications including the removal of organic micropollutants (OMPs). However, the effects of substrates have been overlooked when exploiting and evaluating the efficacy of certain kinds of interlayers in tailoring membrane performance. Herein, a series of TFN membranes were synthesized on different porous substrates with identical interlayers of metal-organic framework nanosheets. It was revealed that the interlayer introduction could narrow but not fully eliminate the difference in the properties among the polyamide layers formed on different substrates, and the membrane performance variation was prominent in distinct aspects. For substrates with small pore sizes exerting severe water transport hindrance, the introduced interlayer mainly enhanced membrane water permeance by affording the gutter effect, while it could be more effective in reducing membrane pore size by improving the interfacial polymerization platform and avoiding PA defects when using a large-pore-size substrate. By matching the selected substrates and interlayers well, superior TFN membranes were obtained with simultaneously higher water permeance and OMP rejections compared to three commercial membranes. This study helps us to objectively understand interlayer efficacies and attain performance breakthroughs of TFN membranes for more efficient water treatment.

Biodegradation kinetics of organic micropollutants in biofilters for advanced wastewater treatment – Impact of operational conditions and biomass origin on removal

Biofiltration processes are often part of advanced wastewater treatment (aWWT) technologies for the removal of organic micropollutants (OMP) from conventional wastewater treatment plant (WWTP) effluents. Although biological effects are not always the main focus of these technologies (e.g. filtration through granular activated carbon), they have been shown to contribute significantly to total OMP removal. While OMP biodegradation kinetics in conventional biological wastewater treatment are well researched, no systematic comparison to biomass from aWWT is available. This biomass faces different growth conditions and higher OMP concentrations relative to the background organic matter. Adaptation to these conditions could be possible and could lead to faster OMP biodegradation kinetics, which would show in a larger pseudo first-order biodegradation kinetic constant kbiol. In this work, kbiol values for biomass obtained from aWWT biofilters were determined by evaluating OMP removals measured in lab-scale biofilters using a mechanistic model of the experimental setup. A comparison to kbiol values from literature for conventional wastewater treatment (with nutrient removal) revealed similar OMP biodegradation kinetics without any advantages of biomass from aWWT. A conceptual evaluation of influencing factors on OMP removal in biofilters showed that operational parameters (such as the biomass concentration or the empty bed contact time) and the affinity of OMPs to adsorb on biomass have a significant additional effect on biological OMP removal. Therefore, kbiol values alone are not sufficient to estimate biological OMP removal in biofilters and further information about the system is required.

Catalytic Ozonation of Pharmaceuticals Using CeO2-CeTiOx-Doped Crossflow Ultrafiltration Ceramic Membranes.

The removal of persistent organic micropollutants (OMPs) from secondary effluent in wastewater treatment plants is critical for meeting water reuse standards. Traditional treatment methods often fail to adequately degrade these contaminants. This study explored the efficacy of a hybrid ozonation membrane filtration (HOMF) process using CeO2 and CeTiOx-doped ceramic crossflow ultrafiltration ceramic membranes for the degradation of OMPs. Hollow ceramic membranes (CM) with a 300 kDa molecular weight cut-off (MWCO) were modified to serve as substrates for catalytic nanosized metal oxides in a crossflow and inside-out operational configuration. Three types of depositions were tested: a single layer of CeO2, a single layer of CeTiOx, and a combined layer of CeO2 + CeTiOx. These catalytic nanoparticles were distributed uniformly using a solution-based method supported by vacuum infiltration to ensure high-throughput deposition. The results demonstrated successful infiltration of the metal oxides, although the yield permeability and transmembrane flow varied, following this order: pristine > CeTiOx > CeO2 > CeO2 + CeTiOx. Four OMPs were examined: two easily degraded by ozone (carbamazepine and diclofenac) and two recalcitrant (ibuprofen and pCBA). The highest OMP degradation was observed in demineralized water, particularly with the CeO2 + CeTiOx modification, suggesting O3 decomposition to hydroxyl radicals. The increased resistance in the modified membranes contributed to the adsorption phenomena. The degradation efficiency decreased in secondary effluent due to competition with the organic and inorganic load, highlighting the challenges in complex water matrices.

Porous β-cyclodextrin polymers for rapid and efficient removal of organic micropollutants from water: The role of sulfonation and porosity on adsorption performance

Removal of organic micropollutants (OMPs) from water, especially hydrophilic and ionized ones, is challenging for water remediation. Herein, porous β-cyclodextrin polymers (PCPs) with tailored functionalization were prepared based on molecular expansion strategy and sulfonation. Partially benzylated β-cyclodextrin was knotted by external crosslinker to form PCP1, and knotting PCP1 by expansion molecule generated PCP2. PCP1 and PCP2 were sulfonated to achieve PCP1–SO3H and PCP2–SO3H. Based on systematical adsorption evaluation toward multiple categories of OMPs, it was found that the introduced strong polar –SO3H group could bring strong hydrogen bonding and electrostatic interactions. PCP2 showed the highest surface (998.97 m2/g) displayed more excellent adsorption performance toward neutral and anionic OMPs, and the adsorption mechanism for this property of PCP2 was dominated by hydrophobic interactions. In addition, the PCP1–SO3H with the lowest surface area (39.75 m2/g) rather than PCP2–SO3H with higher surface (519.28 m2/g) exhibited more superior adsorption towards hydrophilic and cationic OMPs, benefiting by hydrogen bonding and electrostatic interactions as well as appropriate porosity. These results not only confirmed the performance enhancement of PCPs through the integration of novel preparation strategy, but also provided fundamental guidance for PCPs design for water remediation.

Removal of Micropollutants in Water Reclamation by Membrane Filtration: Impact of Pretreatments and Adsorption.

Organic micropollutants (OMPs) present in water and wastewater are in the spotlight because of their potentially harmful effects even at low concentrations and the difficulties of their elimination in urban wastewater treatment plants (UWWTPs). This study explores the impact of some membrane filtration processes on the removal of a group of 11 OMPs with an eye on the effects of two pretreatments (i.e., coagulation and adsorption onto powdered activated carbon (PAC)) and the adsorption of OMPs onto the membranes on the overall removal. For this purpose, ultrafiltration (UF) and nanofiltration (NF) experiments were conducted with selected OMPs spiked in ultrapure water and secondary effluents from UWWTPs. It was observed that the adsorption of OMPs onto the membranes was influenced by the characteristics of the membranes, as well as the presence of effluent organic matter (EfOM). Since adsorption was the dominant mechanism for the rejection of OMPs by UF membranes, a study of the adsorption equilibrium of the micropollutants using UF membrane pieces as the adsorbent was conducted. The adsorption isotherms for the most hydrophobic OMPs fitted the Langmuir model. The efficiency of coagulation and powdered activated carbon (PAC) adsorption coupled with UF were also investigated. Both pretreatments alleviated membrane fouling and improved the rejection of organic and inorganic matter. The PAC pretreatment significantly improved the removal of OMPs in the combined PAC/UF process. The best options for achieving reclaimed water with satisfactory physicochemical quality, nearly devoid of OMPs and microorganisms, and suitable for diverse reuse purposes are either the NF treatment or the combination of PAC/UF.