Micro and nanobubbles-assisted advanced oxidation processes for water decontamination: The importance of interface reactions.

Micro and nanobubbles (MNBs), as an efficient and convenient method, have been widely used in water treatment. Composed of gas and water, MNBs avoid directly introducing potential secondary pollutants. Notably, MNBs exhibit significant advantages through interface reactions in assisting AOPs. They overcome barriers like low mass transfer coefficients and limited reactive sites, and shorten the distance between pollutants and oxidants, achieving higher pollutant removal efficiency. However, there is a lack of systematic summary and in-depth discussion on the fundamental mechanisms of MNBs-assisted AOPs. In this critical review, the characteristics of MNBs related to water treatment are outlined first. Subsequently, the recent applications, performance, and mechanisms of MNBs-assisted AOPs including ozone, plasma, photocatalytic, and Fenton oxidation are overviewed. We conclude that MNBs can improve pollutant removal mainly by enhancing the utilization of reactive oxygen species (ROS) generated by AOPs due to the effective interface reactions. Furthermore, we calculated the electrical energy per order of reaction (EE/O) parameter of different MNBs-assisted AOPs, suggesting that MNBs can reduce the total energy consumption in most of the tested cases. Finally, future research needs/opportunities are proposed. The fundamental insights in this review are anticipated to further facilitate an in-depth understanding of the mechanisms of MNBs-assisted AOPs and supply critical guidance on developing MNBs-based technologies for water treatment.

Indirect photodegradation of typical pyrrolizidine alkaloids in water induced by triplet states of dissolved organic matter.

The occurrence of pyrrolizidine alkaloids (PAs) in the aquatic environment has received growing attention due to their persistent mutagenicity and carcinogenicity. In this study, the photooxidation processes of four representative PAs (senecionine, senecionine N-oxide, europine, and heliotrine) in the presence of dissolved organic matter (DOM) were investigated. The excited triplet DOM (3DOM*) was demonstrated to play a dominant role in the phototransformation of PAs. The observed degradation rates of PAs largely depended on the DOM concentration. Alkaline conditions and the presence of HCO3-/CO32- were conducive to the photodegradation. Based on kinetic modeling, the second-order reaction rate constants of PAs with 3DOM* were predicted to be (1.7∼5.3)×108 M-1 s-1, nearly two orders of magnitude higher than those with singlet oxygen (1O2). The monoester structure and electron-withdrawing substituent (e.g., -O atom) substantially affected the one-electron oxidation potential of PAs, which dictates the reaction rates of PAs with 3DOM*. Finally, a tentative degradation pathway of PAs was proposed, involving the formation of an N-centered radical cation through one-electron transfer, which then likely deprotonated and further oxidized to more persistent and toxic phototransformation products with an added oxygen atom into the pyrrole ring.

Satellite Tracking Reveals the Speed Up of the Lacustrine Algal Bloom Drift in Response to Climate Change.

Satellite evidence indicates a global increase in lacustrine algal blooms. These blooms can drift with winds, resulting in significant changes of the algal biomass spatial distribution, which is crucial in bloom formation. However, the lack of long-term, large-scale observational data has limited our understanding of bloom drift. Here, we have developed a novel method to track the drift using multi-source remote sensing satellites and presented a comprehensive bloom drift data set for four typical lakes: Lake Taihu (China, 2011-2021), Lake Chaohu (China, 2011-2020), Lake Dianchi (China, 2003-2021), and Lake Erie (North America, 2003-2021). We found that blooms closer to the water surface tend to drift faster. Higher temperatures and lower wind speeds bring blooms closer to the water surface, therefore accelerating drift and increasing biomass transportation. Under ongoing climate change, algal blooms are increasingly likely to spread over larger areas and accumulate in downwind waters, thereby posing a heightened risk to water resources. Our research greatly improves the understanding of algal bloom dynamics and provides new insights into the driving factors behind the global expansion of algal blooms. Our bloom-drift-tracking methodology also paves the way for the development of high-precision algal bloom prediction models.

Treatment of high-salinity brine containing dissolved organic matters by vacuum membrane distillation: A fouling mitigation approach via microbubble aeration.

In this study, a laboratory-scale vacuum membrane distillation (VMD) system coupled with microbubble aeration (MBA) was developed for the treatment of high-salinity brine containing organic matters. Herein, at the beginning, feedwater only containing model organics such as humic acid (HA), bovine serum albumin (BSA) and sodium alginate (SA) was utilized to investigate the organic-fouling behavior, results indicated that the permeate flux was not affected by a thin and loose contaminated layer deposited on the membrane surface. Furthermore, dissolved organics in the feed brine inhibited the occurrence of membrane wetting due to the existence of a compact and protective crystals/organic-fouling layer, which can prevent the intrusion of scaling ions into membrane substrates. Besides, organics in the feedwater have a high tendency to adsorb on the membrane surface based on molecular dynamics simulations, thus, forming an organic-fouling layer prior to inorganic scaling. Finally, the effect of MBA on fouling alleviation was evaluated in VMD system, nearly 50% of salt precipitation from fouled membrane was effectively removed with the introduction of MBA, which can be ascribed to a combination of mechanisms, including surface shear forces and electrostatic attractions induced by microbubbles, meanwhile, about 2.2% of the total energy was only consumed, when using MBA. Together, these results demonstrated that MBA was a promising approach to alleviate membrane fouling in VMD.

An innovative S-scheme AgCl/MIL-100(Fe) heterojunction for visible-light-driven degradation of sulfamethazine and mechanism insight.

The development of high efficient photocatalysts for antibiotics contamination in water remains a severe challenge. In this study, a novel step-scheme (S-scheme) photocatalytic heterojunction nanocomposites were fabricated from integrating AgCl nanoparticles on the MIL-100(Fe) octahedron surface through facile multi-stage stirring strategy. The S-scheme heterojunction structure in AgCl/MIL-100(Fe) (AM) nanocomposite provided a more rational utilization of electrons (e-) and holes (h+), accelerated the carrier transport at the junction interface, and enhanced the overall photocatalytic performance of nanomaterials. The visible-light-driven photocatalysts were used to degrade sulfamethazine (SMZ) which attained a high removal efficiency (99.9%). The reaction mechanisms of SMZ degradation in the AM photocatalytic system were explored by electron spin resonance (ESR) and active species capture experiments, which superoxide radical (•O2-), hydroxyl radical (•OH), and h+ performed as major roles. More importantly, the SMZ degradation pathway and toxicity assessment were proposed. There were four main pathways of SMZ degradation, including the processes of oxidation, hydroxylation, denitrification, and desulfonation. The toxicity of the final products in each pathway was lower than that of the parent according to the toxicity evaluation results. Therefore, this work might provide new insights into the environmentally-friendly photocatalytic processes of S-scheme AM nanocomposites for the efficient degradation of antibiotics pollutants.

Mussel-Inspired Immobilization of Photocatalysts with Synergistic Photocatalytic-Photothermal Performance for Water Remediation.

The serious problem of pharmaceutical and personal care product pollution places great pressure on aquatic environments and human health. Herein, a novel coating photocatalyst was synthesized by adhering Ag-AgCl/WO3/g-C3N4 (AWC) nanoparticles on a polydopamine (PDA)-modified melamine sponge (MS) through a facile layer-by-layer assembly method to degrade trimethoprim (TMP). The formed PDA coating was used for the anchoring of nanoparticles, photothermal conversion, and hydrophilic modification. TMP (99.9%; 4 mg/L) was removed in 90 min by the photocatalyst coating (AWC/PDA/MS) under visible light via a synergistic photocatalytic-photothermal performance route. The stability and reusability of the AWC/PDA/MS have been proved by cyclic experiments, in which the removal efficiency of TMP was still more than 90% after five consecutive cycles with a very little mass loss. Quantitative structure-activity relationship analysis revealed that the ecotoxicities of the generated intermediates were lower than those of TMP. Furthermore, the solution matrix effects on the photocatalytic removal efficiency were investigated, and the results revealed that the AWC/PDA/MS still maintained excellent photocatalytic degradation efficiency in several actual water and simulated water matrices. This work develops recyclable photocatalysts for the potential application in the field of water remediation.

Double photoelectron-transfer mechanism in Ag-AgCl/WO3/g-C3N4 photocatalyst with enhanced visible-light photocatalytic activity for trimethoprim degradation.

Antibiotic contamination is increasing scrutinized recently. In this work, the Ag-AgCl/WO3/g-C3N4 (AWC) nanocomposites were successfully synthesized using a two-step process involving electrostatic self-assembly and in-situ deposition for trimethoprim (TMP) degradation. The as-prepared photocatalysts were investigated and characterized by XRD, FTIR, XPS, TGA, SEM, TEM, UV-vis, PL and EIS. The experimental results indicated that 99.9% of TMP (4 mg/L) was degraded within 60 min when the concentration of AWC was 0.5 g/L. Reactive species scavenging experiments and electron spin resonance (ESR) experiments illustrated that superoxide radical (•O2-) and photogenerated holes (h+) were the main active species. The functional theory calculation and identification of intermediates via HPLC-MS revealed the possible degradation pathways of TMP. A double photoelectron-transfer mechanism in AWC photocatalyst was proposed. Five cycling photocatalytic tests and reactions under different solution matrix effects further supported that the AWC was a promising photocatalyst for the removal of TMP from the aquatic environment.

Simultaneous removal of harmful algal cells and toxins by a Ag2CO3-N:GO photocatalyst coating under visible light.

The frequent harmful algae blooms (HABs) in eutrophic waters pose serious threats to the water environment and health of human beings and animals. In this study, a new type of photocatalytic coating was prepared by loading Ag2CO3-N:GO (AGON) on the polyurethane sponge modified by silica sol via a dip coating method for the photocatalytic inactivation of Microcystis aeruginosa (M. aeruginosa) and degradation of Microcystin-LR (MC-LR). The factors including photocatalyst loading dosage, natural organic matter (NOM), and alkalinity were studied. The effects on the physiological characteristics of M. aeruginosa and reactive oxygen species (ROS) were also investigated to reveal the photocatalytic inactivation mechanisms. The results showed that the AGON coating-4 (the initial concentration of AGON suspension used for loading is 4 g/L) exhibited the optimum photocatalytic performance under visible light, which can completely remove chlorophyll a after 5 h of irradiation. And the NOM and alkalinity in water have relatively negative effects on the photocatalytic inactivation of algae. The prepared AGON coating also exhibited excellent photocatalytic performance in the degradation of MC-LR under visible light. It only needed 20, 60 and 120 min to completely degrade 0.1, 0.3 and 0.5 mg/L MC-LR, respectively. However, the mixed systems of algae and MC-LR required a longer time to achieve photocatalytic degradation. The O2- were the predominant reactive oxygen species, causing the damage of cell membranes and walls and the leakage of cellular content, which eventually led to the irreversible damage to algal cells. What's more, the coating can be reused several times due to its good cyclability and stability. Therefore, the AGON coating has promising prospects for the treatment of algal blooms in eutrophic waters.