Degradation Of Micropollutants Research Articles

Dissolved Organic Matter-Mediated Photosensitized Activation of Monochloramine for Micropollutant Abatement in Wastewater Effluent.

Utilizing solar light and water matrix components in situ to reduce the chemical and energy demands would make treatment technologies more sustainable for micropollutant abatement in wastewater effluents. We herein propose a new strategy for micropollutant abatement through dissolved organic matter (DOM)-mediated photosensitized activation of monochloramine (NH2Cl). Exposing the chlorinated wastewater effluent with residual NH2Cl to solar irradiation (solar/DOM/NH2Cl process) degrades six structurally diverse micropollutants at rate constants 1.26-34.2 times of those by the solar photolysis of the dechlorinated effluent (solar/DOM process). Notably, among the six micropollutants, the degradation rate constants of estradiol, acetaminophen, bisphenol A, and atenolol by the solar/DOM/NH2Cl process are 1.13-4.32 times the summation of those by the solar/DOM and solar/NH2Cl processes. The synergism in micropollutant degradation is attributed to the generation of reactive nitrogen species (RNS) and hydroxyl radicals (HO·) from the photosensitized activation of NH2Cl. Triplet state-excited DOM (3DOM*) dominates the activation of NH2Cl, leading to the generation of RNS, while HO· is produced from the interactions between RNS and other photochemically produced reactive intermediates (e.g., O2·- and DOM·+/·-). The findings advance the knowledge of DOM-mediated photosensitization and offer a sustainable method for micropollutant abatement in wastewater effluents containing residual NH2Cl.

Visible-light-assisted peroxymonosulfate activation by metal-free g-C3N4 isotype heterojunction for water purification: Surface-activated complex and 1O2 dominated non-radical mechanisms

Visible-light-assisted peroxymonosulfate (PMS) activation is flourishing in wastewater decontamination, but exploiting safe and efficient activators remains challenging due to a deficient cognition of the activated mechanisms. Hereby, a metal-free g-C3N4 isotype heterojunction (HCN) was successfully synthesized and activated PMS under visible light. The Z-scheme isotype heterojunction significantly meliorated light absorption and carrier migration, thereby enhancing PMS activation. The optimal HCN + PMS system almost completely removed ranitidine (RAN) in 30 min with 7.46–8.48 times higher activity than the monomers. Through systematic experiments and characterizations, we proposed a non-radical mechanism of PMS activation, which generated predominated surface-activated complex and singlet oxygen (1O2) for pollutant removal. The surface-activated complex degraded RAN by drawing its electrons. This non-radical pathway exhibited tolerance towards background substances and pH fluctuations. Additionally, the broad-spectrum decontamination and recyclability of the system further enhanced its practical applicability. Notably, intermediate analyses confirmed the RAN degradation pathways predicted by theoretical calculations, with the resulting intermediates found to be non-toxic. This study significantly contributes to our understanding of the non-radical mechanisms of PMS activation on g-C3N4-based activators for micropollutant degradation.

Bubble-less photocatalytic ozonation with ceramic membranes and static mixers enhances the total organic carbon removal and degradation of iodinated X-ray contrast agents

Conventional bubble-based ozonation of wastewater creates several issues, e.g., the low degradation of certain micropollutants like X-ray contrast agents, mass transfer limitations due to inhomogeneous mixing, and the waste of undissolved ozone. In contrast, this work uses tubular ceramic membranes for bubble-free and bubble-less ozonation. Static mixers are placed around the membrane to enhance the radial mixing of ozone, creating homogeneous reaction conditions throughout the membrane contactor. Additionally, the ozone mass transfer significantly increases with static mixers. Furthermore, the membrane is made of a photocatalyst (TiO2) on the shell-side to improve the micropollutant degradation by photocatalytic ozonation. An ozone-stable hydrophobic treatment method is developed to use ceramic membranes as a membrane contactor for the ozonation of water. After hydrophobic treatment, the ozone mass transfer coefficient is in the order of 1.3 ⋅ 10−6 ms−1 using bubble-less operation resulting in an ozone concentration up to 4.0 mg L−1. Overall, bubble-less operation significantly increases the ozone mass transfer compared to bubble-free operation. Photocatalytic ozonation in a membrane contactor with static mixers increases the degradation of diatrizoate by 37% compared to sole ozonation in the same membrane contactor. Furthermore, this process increases the removal of total organic carbon in experiments with a water matrix consisting of four different micropollutants by 115% compared to sole ozonation.

Efficient electro-Fenton degradation of organic pollutants via the synergistic effect of 1O2 and •OH generated on single Fe[sbnd]N4 sites

The electro-Fenton with in situ generated 1O2 and •OH is a promising method for the degradation of micropollutants. However, its application is hindered by the lack of catalysts that can efficiently generate 1O2 and •OH from electrochemical oxygen reduction. Herein, N-doped stacked carbon nanosheets supported Fe single atoms (Fe-NSC) with FeN4 sites were designed for simultaneous generation of 1O2 and •OH to enhance electro-Fenton degradation. Due to the synergistic effect of 1O2 and •OH, a variety of contaminants (phenol, 2,4-dichlorophenol, sulfamethoxazole, atrazine and bisphenol A) were efficiently degraded with high kinetic constants of 0.037–0.071 min−1 by the electro-Fenton with Fe-NSC as cathode (−0.6 V vs Ag/AgCl, pH 6). Moreover, the superior performance for electro-Fenton degradation was well maintained in a wide pH range from 3 to 10 even with interference of various inorganic salt ions. It was found that FeN4 sites with pyridinic N coordination were responsible for its good performance for electro-Fenton degradation. Its 1O2 yield was higher than •OH yield, and the contribution of 1O2 was more significant than •OH for pollutant degradation.

Effect of multi-walled carbon nanotubes properties on the photocatalytic activity of bismuth-based composites synthesised via an imidazolium ionic liquid

The use of various types of multi-walled carbon nanotubes in the synthesis of bismuth oxybromide semiconductors via imidazolium ionic liquid was studied in detail. The effect of the MWCNT shape, specific surface area, and various diameters on the morphology, surface properties and photoactivity of the Bi-based composites has been investigated for the first time. So far, the literature has only shown the enhancement of photocatalytic activity of composites containing MWCNT; however, our research shows a broader view of the issue. The photocatalytic activity of the individual composites under UV–Vis irradiation was assessed by the degradation of various micropollutants, showing the diversity of properties of the obtained composites. It is also significant that in the composite system, the imidazolium ionic liquid played a crucial role in the formation of microspheres and acted as a dispersing agent, leading to an even distribution of MWCNTs on the surface of the spherical bismuth oxybromide.

Electrochemical UV/Ozone process with Ni-Sb-SnO2/SiOx anode for degradation of micropollutants in wastewater

We investigated the synergistic effects of ozone evolution reaction (OZER) coupled with UV irradiation for degradation of O3-refractory micro-pollutants in electrochemical (E)-UV/O3 process. A SiOx heterojunction layer over-coated on Ni-Sb-SnO2 remarkably enhanced the OZER across a wide pH range (0.4–10). The exceptional OZER efficiency was harnessed in E-UV/O3 to increase degradation rates (by 2.5–3.5-fold) and mineralization efficiencies (by 1.3–3.9-fold) for 2,6-dinitrotoluene (DNT) compared to the sums under dark electrolysis and photolysis. Clarifying DNT degradation intermediates and reactive oxygen species elucidated the promoting mechanism within the reaction network of O3 transformation to ∙OH, the principal oxidant for the supreme performance at near-neutral pH. Applicability of E-UV/O3 was demonstrated by minuscule halate ion generation, outstanding stability and energy efficiency, and elimination of N,N-diethyl-m-toluamide (DEET) in reverse osmosis concentrates (ROC). These comprehensive findings from mechanistic studies to real applications are expected to broaden the utilization of OZER-based water treatments.

Reactive layered hydroxide membrane for advanced water treatment: Micropollutant degradation and antifouling potential

The effective removal of micropollutants by water treatment technologies remains a significant challenge. Herein, we develop a CoFe layered double hydroxide (CoFeLDH) catalytic membrane for peroxymonosulfate (PMS) activation to achieve efficient micropollutant removal with improved mass transfer rate and reaction kinetics. This study found that the CoFeLDH membrane/PMS system achieved an impressive above 98% degradation of the probe chemical ranitidine at 0.1 mM of PMS including five more micropollutants (Sulfamethoxazole, Ciprofloxacin, Carbamazepine, Acetaminophen and Bisphenol A) at satisfactory level (above 80%). Moreover, significant improvements in water flux and antifouling properties were observed, marking the membrane as a specific advancement in the removal of membrane fouling in water purification technology. The membrane demonstrated consistent degradation efficiency for several micropollutants and across a range of pH (4–9) as well as different anionic environments, thereby showing it suitability for scale-up application. The key role of reactive species such as SO4•–, and O2• − radicals in the degradation process was elucidated. This is followed by the confirmation of the occurrence of redox cycling between Co and Fe, and the presence of CoOH+ that promotes PMS activation. Over the ten cycles, the membrane could be operated with a flux recovery of up to 99.8% and maintained efficient performance over 24 h continuous operation. Finally, the efficiency in degrading micropollutants, coupled with reduced metal leaching, makes the CoFeLDH membrane as a promising technology for application in water treatment.

Photo-assisted natural chalcopyrite activated peracetic acid for efficient micropollutant degradation

The effective activation of natural chalcopyrite (CuFeS2) on peracetic acid (PAA) to remove organic micropollutants was studied under visible light irradiation. Results showed than an effective sulfamethoxazole (SMX) degradation (95.0 %) was achieved under visible light irradiation for 30 min at pH 7.0. Quenching experiments, electron spin resonance analysis, and LC/MS spectrum demonstrated that HO• and CH3C(O)OO• were the main reactive species for SMX degradation, accounting for 43.3 % and 56.7 % of the contributions, respectively. Combined with X-ray photoelectron spectroscopy analysis, the photoelectrons generated on CuFeS2 activated by visible light enhanced the Fe3+/Fe2+ and Cu2+/Cu+ cycles on the surface, thereby activating PAA to generate HO•/CH3C(O)OO•. The removal rate of SMX decreased with the increase in wavelengths, due to the formation of low energy photons at longer wavelengths. Besides, the optimal pH for degradation of SMX by CuFeS2/PAA/Vis-LED process was neutral, which was attributed to the increasing easily activated anionic form of PAA during the increase in pH and the depletion of Fe species at alkaline conditions. Cl−, HCO3−, and HA slightly inhibited SMX degradation because of reactive species being quenched and/or shielding effect. Furthermore, the degradation efficiency of different pollutants by CuFeS2/PAA/Vis-LED was also measured, and the removal efficiency was different owing to the selectivity of CH3C(O)OO•. Finally, the process exhibited good applicability in real waters. Overall, this study provides new insight into visible light-catalyzed activation of PAA and suggests on further exploration of the intrinsic activation mechanism of PAA.

Protecting against micropollutants in water storage tanks using in-situ TiO2 coated quartz optical fibers

Photocatalyst-coated optical fibers (P-OFs) using UV-A LEDs offer a highly promising solution for the degradation of micropollutants within municipal, reuse, industrial or home distribution systems, by integrating P-OFs into water storage tanks. P-OFs have photocatalysts attached to bundles of optical fibers, enabling their direct deployment within tanks. This eliminates the necessity for photocatalyst slurries, which would require additional membrane or separation systems. However, a current limitation of P-OFs is light management, specifically light oversaturation of the coated photocatalysts and short light transmission distances along fibers. This study overcomes this limitation and reveals strategies to improve the light dissipation uniformity along P-OFs, and demonstrates the performance of P-OFs on degrading a model micropollutant, carbamazepine (CBZ). Key tunable variables of fibers and light emission conditions, including photocatalyst coating patchiness (p), minimum light incident angles (θm), radiant flux launched to fibers (Φi), and fiber diameters (D), were modeled to establish their relationships with the light dissipation uniformity in TiO2-coated quartz optical fibers (TiO2-QOFs). We then validated modeling insights by conducting experiments to examine how these variables influence the generation of evanescent waves which are localized energy on fiber surfaces, leading to either photocatalyst activation or the recapture of unused light back into fibers. We observed substantial enhancements in evanescent waves generation by decreasing p and increasing θm, resulting in uniform light dissipation which reduces light oversaturation and improves light transmission distances. Moreover, these optimizations led to a remarkable three-fold improvement in CBZ degradation rates and a 65% reduction in energy consumption. Such improvement substantially reduces the capital and operational cost and enhances practicality of energy-efficient photocatalysis without additional chemical oxidants for micropollutant degradation in water storage tanks.

Biological degradation of organic micropollutants in GAC filters–temporal development and spatial variations

The capacity for organic micropollutant removal in granular activated carbon (GAC) filters for wastewater treatment changes over time. These changes are in general attributed to changes in adsorption, but may in some cases also be affected by biological degradation. Knowledge on the degradation of organic micropollutants, however, is scarce. In this work, the degradation of micropollutants in several full-scale GAC and sand filters was investigated through incubation experiments over a period of three years, using 14C-labeled organic micropollutants with different susceptibilities to biological degradation (ibuprofen, diclofenac, and carbamazepine), with parallel 16S rRNA gene sequencing. The results showed that the degradation of diclofenac and ibuprofen in GAC filters increased with increasing numbers of bed volumes when free oxygen was available in the filter, while variations over filter depth were limited. Despite relatively large differences in bacterial composition between filters, a degradation of diclofenac was consistently observed for the GAC filters that had been operated with high influent oxygen concentration (DO >8 mg/L). The results of this comprehensive experimental work provide an increased understanding of the interactions between microbial composition, filter material, and oxygen availability in the biological degradation of organic micropollutants in GAC filters.

Innovative mapping of groundwater redox status and cation exchange conditions in a GIS environment

Understanding the complexities of regional groundwater quality is crucial for managing groundwater resources. Groundwater quality assessment involves investigating specific dissolved groundwater components, for example, comparing them to established standards. To fully understand all aspects of groundwater quality, one should assess composite properties, one being the redox status and another being the cation exchange condition. The first may, for example, impose a control on the degradation of organic micropollutants. While groundwater numerical indices can be easily interpolated and visualised using various GIS applications, consistently mapping the redox status and cation exchange conditions as non-numerical indices remains challenging. Furthermore, no study has yet conducted a regional-scale mapping of cation exchange classes in a GIS environment using extensive groundwater samples. To deepen our understanding of these groundwater components, we employed ArcGIS in this study to map the redox and cation exchange conditions in two stages. First, we mapped the groundwater components of interest, including Cl, SO4, SO4/Cl, Fe, NO3 and base exchanges of Na and Mg, by the most appropriate interpolation method identified by a geostatistical analysis. Then, variables were combined, and the conditional functions were used in ArcMap's Math toolbox to determine redox status or cation exchange classes. Our innovative GIS method for mapping regional redox status and cation exchange conditions was developed for 3350 groundwater sampling locations in the coastal lowlands of the Western Netherlands. The method was successful, with generally 75%–95% similarity between predicted and observed situations for most classes. The introduced method is more straightforward than others and can map other non-numerical linguistic indices like Wilcox groundwater and irrigation water classifications, as well.

Enzymatic degradability of diclofenac ozonation products: A mechanistic analysis

The treatment of waterborne micropollutants, such as diclofenac, presents a significant challenge to wastewater treatment plants due to their incomplete removal by conventional methods. Ozonation is an effective technique for the degradation of micropollutants. However, incomplete oxidation can lead to the formation of ecotoxic by-products that require a subsequent post-treatment step. In this study, we analyze the susceptibility of micropollutant ozonation products to enzymatic digestion with laccase from Trametes versicolor to evaluate the potential of enzymatic treatment as a post-ozonation step. The omnipresent micropollutant diclofenac is used as an example, and the enzymatic degradation kinetics of all 14 detected ozonation products are analyzed by high-performance liquid chromatography coupled with high-resolution mass spectrometry (HPLC-HRMS) and tandem mass spectrometry (MS2). The analysis shows that most of the ozonation products are responsive to chemo-enzymatic treatment but show considerable variation in enzymatic degradation kinetics and efficiencies. Mechanistic investigation of representative transformation products reveals that the hydroxylated aromatic nature of the ozonation products matches the substrate spectrum, facilitating their rapid recognition as substrates by laccase. However, after initiation by laccase, the subsequent chemical pathway of the enzymatically formed radicals determines the global degradability observed in the enzymatic process. Substrates capable of forming stable molecular oxidation products inhibit complete detoxification by oligomerization. This emphasizes that it is not the enzymatic uptake of the substrates but the channelling of the reaction of the substrate radicals towards the oligomerization of the substrate radicals that is the key step in the further development of an enzymatic treatment step for wastewater applications.

Microbial synergies drive simultaneous biodegradation of ethoxy and alkyl chains of Nonylphenol Ethoxylate in fluidized bed reactors

The widely-used surfactant Nonylphenol Ethoxylate (NPEO) produces endocrine-disrupting compounds during biodegradation, with these byproducts being more harmful than untreated NPEO. This study investigates the effectiveness of a Fluidized Bed Reactor (FBR) in reducing the production of 4-Nonylphenol (4-NP) during the biodegradation of NPEO. Two identical FBR filled with sand were used to assess the NPEO degradation and to enhance the microbial consortia capable of breaking down the complex byproducts, ethanol and fumarate were introduced as co-substrates. Our findings demonstrate the significant potential of the FBR, especially when coupled with fumarate, for enhancing the surfactant degradation. It outperforms the efficiency achieved with ethanol as the primary electron donor, albeit with a higher rate of byproduct production. Microbial community taxonomy and metabolic prediction revealed the high abundance of Geobacter (1.51–31.71%) and Methanobacterium (1.08–13.81%) in non-conductive sand. This may hint a new metabolic interaction and expand our understanding of Direct Interspecies Electron Transfer (DIET) in bioreactors applied to micropollutants degradation. Such an intricate relationship between facultative and anaerobes working together to simultaneously biodegrade the ethoxy and alkyl chains presents a new perspective on NPEO degradation and can potentially be extended to other micropollutants.

Elucidating the enhanced role of carbonate radical in propranolol degradation by UV/peroxymonosulfate system

Carbonate radical (CO3•−) has been proved to be an important secondary radical in advanced oxidation processes due to various radical reactions involved HCO3−/CO32−. However, the roles and contributions of CO3•− in organic micropollutant degradation have not been explored systematically. Here, we quantified the impact of CO3•− on the degradation kinetics of propranolol, a representative pollutant in the UV/peroxymonosulfate (PMS) system, by constructing a steady-state radical model. Substantially, the measured values were coincident with the predictive values, and the contributions of CO3•− on propranolol degradation were the water matrix-dependent. Propranolol degradation increased by 130% in UV/PMS system containing 10 mM HCO3−, and the contribution of CO3•− was as high as 58%. Relatively high pH values are beneficial for propranolol degradation in pure water containing HCO3−, and the contributions of CO3•− also enhanced, while an inverse phenomenon was shown for the effects of propranolol concentrations. Dissolved organic matter exhibited significant scavenging effects on HO•, SO4•−, and CO3•−, substantially retarding the elimination process. The developed model successfully predicted oxidation degradation kinetics of propranolol in actual sewage, and CO3•− contribution was up to 93%, which in indicative of the important role of CO3•− in organic micropollutant removal via AOPs treatment.

On the geometry and material stability of tubular PVDF-TiO2 static mixer membrane contactors for photocatalytic ozonation of micropollutants

The prevention of ozone hotspots in ozonation reactors for wastewater treatment is essential for effective degradation of micropollutants without forming harmful by-products. Membrane contactors can provide a bubble-free ozonation process that is able to decrease by-product formation, e.g., bromate formation in bromide-charged wastewater. Furthermore, the geometry of the reactor influences the distribution of dissolved ozone in a membrane contactor. Turbulence promoters can significantly decrease ozone hotspots and increase ozone mass transfer into wastewater. This work presents a fabrication methodology to produce PVDF-TiO2 helical static mixer membranes using the rotation-in-a-spinneret technology. Static mixer membranes combine the functionality of a membrane contactor and a static mixer in a single component. Furthermore, the PVDF matrix is doped with TiO2 particles as photocatalyst. Thus, we present a membrane-based photocatalytic ozonation process to increase the concentration of hydroxyl radicals for degradation of micropollutants under UV radiation. Static mixer membranes increase the ozone mass transfer coefficient by 70% compared to conventional hollow fiber membranes. Furthermore, the specific photocatalytic degradation rate of methylene blue increases by 50% using static mixer membranes. However, this work also reveals a lack of long-term stability of PVDF-TiO2 membranes in the corrosive environment of photocatalytic ozonation. The molecular weight of PVDF decreases by 11% after use in photocatalytic ozonation resulting in a loss of mechanical stability of the membranes. Similar material concepts are required based on ceramic materials which avoid wetting of the porosity.

Regulating charge transfer for enhanced PAA activation over sulfur-doped magnetic CoFe2O4: A novel strategy for simultaneous micropollutants degradation and bacteria inactivation

Micropollutants and bacteria are prevalent pollutants in wastewater, posing significant risks to ecosystems and human health. As peracetic acid (PAA) is being increasingly used as a disinfectant, activation of PAA by low-cost and high-performance activators is a promising strategy for wastewater treatment. In this study, the sulfur-doped magnetic CoFe2O4 (SCFO) is successfully developed for efficient PAA activation to simultaneously decontaminate and disinfect wastewater. PAA/SCFO-0.3 exhibits exceptional performance, degrading 100 % of 8 μM sulfamethoxazole (SMX) with a first-pseudo reaction rate of 1.275 min−1, and achieving 5.3-log inactivation of Escherichia coli (E. coli) within 3 min at a PAA dosage of 0.2 mM and catalyst dosage of 0.025 g/L (initial pH 6.5). Scavenging experiments and electron paramagnetic resonance (EPR) analysis identify CH3C(O)O• and CH3C(O)OO• as the dominant reactive species for SMX degradation. The sulfur species in SCFO-0.3 facilitate Co2+ regeneration and regulate charge transfer, promoting PAA activation for SMX degradation. Moreover, the PAA/SCFO-0.3 system demonstrates operational feasibility over a broad range of water matrices and has excellent stability and reusability (maintaining 93 % removal of SMX after 5 cycles), demonstrating its potential for industrial applications. This study provides insights into enhancing PAA activation through sulfur doping in transition metal catalysts and highlights the practical applicability of the PAA/SCFO-0.3 system as an advanced alternative to conventional disinfection for simultaneous decontamination and disinfection in wastewater.

Simulated solar light-driven degradation of micropollutant in water by biochar-based metal-free catalyst: Regulation strategies for electronic structure and morphology engineering

The biochar/h-BN/g-C3N4 (BNC) composite photocatalyst with a spherical sheet cluster structure, was successfully synthesized. Under simulated solar light irradiation, the photocatalytic degradation rate of reactive red 120 by BNC was 87.94 % within 90 min, corresponding to a 3.57-fold higher kinetic constant than that of g-C3N4. The band structure and electron transfer path in BNC were determined using characterizations and density functional theory (DFT) calculations, confirming a type II heterojunction forming. The attraction of h-BN to h+ by electrostatic interaction and biochar's capacity for both electron transfer and storage were confirmed. Doping of biochar was also found to enhance light absorption and provide O vacancy. The existence of piezoelectric effect assisted the movement of photogenerated carriers to the material surface. In the system, the main active oxidation species were h+ and ·O2–. By calculating optical characteristics, the practical activity of photocatalysts is evaluated. Results indicated that the optimal dosage of BNC was 0.5 g/L in the planar reactor, corresponding to an optical thickness of 2.61 calculated by the six-flux radiation absorption–scattering model (SFM). Biochar doping was found to enhance light absorption. A novel photocatalytic mechanism was proposed for promising matel-free BNC.

Degradation of imidazolium-based ionic liquids by UV photolysis and pulsed corona discharge: The effect of persulfates addition

Ionic liquids (ILs) are salts with exceptional properties important for future development, although potentially hazardous for humans and aquatic life due to their high aqueous solubility and toxicity. Biodegradation of ILs depends on the anion nature and cation structure: many ILs are not readily degraded during conventional wastewater treatment, thus requiring alternative cost-effective and energy-efficient solutions. In this research, the degradation of aqueous imidazolium-based ILs by pulsed corona discharge (PCD) and UV photolysis combined with persulfates was studied, using peroxymonosulfate (PMS) and peroxydisulfate (PDS) as extrinsic oxidants. 1-Ethyl-3-methylimidazolium chloride ([Emim][Cl]), 1-methyl-3-octylimidazolium chloride ([Omim][Cl]), and 1-ethyl-3-methylimidazolium bromide ([Emim][Br]) were chosen as imidazolium-based ILs with different alkyl chain lengths and anions in oxidation experiments under variable operation factors - pH, concentrations of persulfates, pulse repetition frequency in PCD. Pulsed corona discharge has previously shown high energy efficiency in the degradation of micropollutants but has not yet been applied to ionic liquids. The experimental results showed the ability of PCD, PCD/oxidant and UV/oxidant combinations to completely degrade the ILs with the degradation rates in descending order [Emim][Cl] > [Omim][Cl] > [Emim][Br], indicating an impact of both the alkyl chain length and the type of anion on the oxidation rate. The strong activation of persulfates was observed in UV/oxidant combinations, whereas PCD demonstrated the effect of persulfates addition between slight acceleration and moderate deceleration of oxidation dependent on the concentration of extrinsic oxidants. The addition of the sulfate radicals’ scavenger, however, showed the presence of those in all combinations indicating a certain replacement of PCD-generated reactive oxygen species with secondary reactants formed from persulfates. The unassisted PCD and UV/PDS combination demonstrated similar energy efficiencies of about 54 and 26 mmol kWh−1 for [Emim][Cl] and [Emim][Br] degradation, respectively, while for [Omim][Cl] the UV/PDS combination showed energy efficiency 1.42 times higher than unassisted PCD.

Fast sintering of titania monoliths for photocatalytic degradation of organic micropollutants

Scalable solutions to efficiently remove organic micropollutants from water are urgently needed to address the significant adverse health effects their accumulation causes on the environment and in humans. Solutions based on slurries of titania (TiO2) nanoparticles, while effective in the lab, cannot be scaled up due to cost and environmental concerns. Conversely, titania monolithic structures are not photoactive as high sintering temperatures result in the predominance of the non-photoactive rutile phase. In this work the combination of 3D printing and fast sintering allowed, for the first time, to obtain titania monoliths which are mechanically stable and retain their photoactivity. The latter arises from the anatase-rich composition of the monoliths, a result not possible using convectional sintering methods. To demonstrate their photoactivity, the porous monoliths were used in a recirculating flow reactor to degrade primidone, a widely used drug and ubiquitous micropollutant. Results for the best performing monolith showed a quantum yield value of 1.1 × 10−5and an electrical energy per order value of 13 kWh m−3, both significantly outperforming literature data. These results show a clear route to scaling-up the fabrication of photocatalytically active titania monoliths capable of effectively degrading organic micropollutants in water, whose presence is a major health and environmental hazard.

Far-UVC Photolysis of Peroxydisulfate for Micropollutant Degradation in Water.

Increasing radical yields to reduce UV fluence requirement for achieving targeted removal of micropollutants in water would make UV-based advanced oxidation processes (AOPs) less energy demanding in the context of United Nations' Sustainable Development Goals and carbon neutrality. We herein demonstrate that, by switching the UV radiation source from conventional low-pressure UV at 254 nm (UV254) to emerging Far-UVC at 222 nm (UV222), the fluence-based concentration of HO• in the UV/peroxydisulfate (UV/PDS) AOP increases by 6.40, 2.89, and 6.00 times in deionized water, tap water, and surface water, respectively, with increases in the fluence-based concentration of SO4•- also by 5.06, 5.81, and 55.47 times, respectively. The enhancement to radical generation is confirmed using a kinetic model. The pseudo-first-order degradation rate constants of 16 micropollutants by the UV222/PDS AOP in surface water are predicted to be 1.94-13.71 times higher than those by the UV254/PDS AOP. Among the tested water matrix components, chloride and nitrate decrease SO4•- but increase HO• concentration in the UV222/PDS AOP. Compared to the UV254/PDS AOP, the UV222/PDS AOP decreases the formation potentials of carbonaceous disinfection byproducts (DBPs) but increases the formation potentials of nitrogenous DBPs.