Mechanistic insight into humic acid-enhanced sonophotocatalytic removal of 17ß-estradiol: Formation and contribution of reactive intermediates.

In this study, humic acid (HA) enhanced 17ß-estradiol (17ß-E2) degradation by Er3+-CdS/MoS2 (ECMS) was investigated under ultrasonic and light conditions. The degradation reaction rate of 17ß-E2 was increased from (14.414 ± 0.315) × 10-3 min-1 to (122.677 ± 1.729) × 10-3 min-1 within 90 min sonophotocatalytic (SPC) reaction with the addition of HA. The results of quenching coupled with chemical probe experiments indicated that more reactive intermediates (RIs) including reactive oxygen species (ROSs) and triplet-excited states were generated in the HA-enhanced sonophotocatalytic system. The triplet-excited states of humic acid (3HA*), hydroxyl radical (•OH), and superoxide radical (•O2-) were the dominant RIs for 17ß-E2 elimination. In addition, the energy- and electron-transfer process via coexisting HA also account for 12.86% and 29.24% contributions, respectively. The quantum yields of RIs in the SPC-ECMS-HA system followed the order of 3HA* > H2O2 > 1O2 > â€¢O2-> •OH. Moreover, the spectral and fluorescence characteristics of HA were further analyzed during the sonophotocatalytic reaction process. The study expanded new insights into the comprehension of the effects of omnipresent coexisting HA and RIs formation for the removal of 17ß-E2 during the sonophotocatalytic process.

Migration and abiotic transformation of estrone (E1) and estrone-3-sulfate (E1-3S) during soil column transport.

Steroid estrogens have received worldwide attention and given rise to great challenges of aquatic ecosystems security, posing potential adverse effects on aquatic organisms and human health even at low levels (ng/L). The present study focused on understanding the mobility and abiotic transformation of estrone (E1) and estrone-3-sulfate (E1-3S) over spatial and time scales during soil transport. Column transport experiments showed that the migration capacity of E1-3S was far stronger than E1 in soil. The calculated groundwater ubiquity score and leachability index values also indicated the high leaching mobility of E1-3S. The hydrolysis of E1-3S and abiotic transformation into estradiol and estriol was observed in the sterilized soil. Furthermore, possible transformation products (e.g., SE239, E2378, E1 dimer538, E1-E2 dimer541) of E1 and E1-3S in soil were analyzed and identified after the column transport experiments. The estrogenic activity was estimated by 17ß-estradiol equivalency values during the transport process in aqueous and soil phases. Additionally, the potential leaching transport to groundwater of E1-3S requires further critical concern.

Magnetically separable ZnFe2O4/Ag3PO4/g-C3N4 photocatalyst for inactivation of Microcystis aeruginosa: Characterization, performance and mechanism.

Water eutrophication leads to increasingly serious harmful algal blooms (HABs), which poses tremendous threats on aquatic environment and human health. In this work, a novel magnetically separable ZnFe2O4/Ag3PO4/g-C3N4 (ZFO/AP/CN) photocatalyst with double Z-scheme was constructed for Microcystis aeruginosa (M. aeruginosa) inactivation and Microcystin-LR (MC-LR) degradation under visible light. The photocatalyst was characterized by XRD, SEM, EDS, TEM, XPS, FTIR, UV-vis, PL, and VSM. Approximately 96.33% of chlorophyll a was degraded by ZFO/AP/CN (100 mg/L) after 3 h of visible light irradiation. During the photocatalytic process, the malondialdehyde (MDA) of M. aeruginosa increased, the activities of superoxide dismutase (SOD) and catalase (CAT) increased initially and decreased afterwards. Furthermore, the photocatalytic removal efficiency of M. aeruginosa (OD680 ≈0.732) and MC-LR (0.2 mg/L) reached 94.31% and 76.92%, respectively, in the simultaneous removal of algae and algal toxin experiment. Reactive species scavenging experiments demonstrated that·O2- and·OH played key roles in inactivating M. aeruginosa and degrading MC-LR. The excellent recoverability and stability of ZFO/AP/CN were proved by cycling photocatalytic experiment which using magnetic recovery method. In summary, the synthesized magnetically separable ZFO/AP/CN photocatalyst has remarkable photocatalytic activity under visible light and shows promising potential for practical application of alleviating HABs.

Sono-photo hybrid process for the synergistic degradation of levofloxacin by FeVO4/BiVO4: Mechanisms and kinetics.

A novel FeVO4/BiVO4 heterojunction photocatalyst was synthesized by hydrothermal method. The FeVO4/BiVO4 nanostructures were characterized by XRD, SEM, XPS, UV-vis, and photoluminescence spectroscopy. The effects of catalyst dosage, contaminant concentration, initial hydrogen peroxide (H2O2) concentration, and pH value on the degradation of levofloxacin were investigated and several repeated experiments were conducted to evaluate the stability and reproducibility. The optimized process parameters were used for mineralization experiments. Reactive oxygen species, degradation intermediates, and possible catalytic mechanisms were also investigated. The results showed that the sonophotocatalytic performance of the FeVO4/BiVO4 heterojunction catalyst was better than that of sonocatalysis and photocatalysis. In addition, the Type II heterojunction formed by the material still had good stability in the degradation of levofloxacin after 5 cycles. The possible degradation pathway and mechanism of levofloxacin by sonophotocatalysis were put forward. This work develops new sono-photo hybrid process for potential application in the field of wastewater treatment.

Self-floating photocatalytic hydrogel for efficient removal of Microcystis aeruginosa and degradation of microcystins-LR.

Cyanobacterial harmful algal blooms (CyanoHABs) and the release of cyanotoxins have posed adverse impacts to aquatic system and human health. In this study, a novel self-floating Ag/AgCl@LaFeO3 (ALFO) photocatalytic hydrogel was prepared via freeze-thaw method for removal of Microcystis aeruginosa (M. aeruginosa). The ALFO hydrogel performed an excellent photocatalytic activity with a 99.4% removal efficiency of chlorophyll a within 4 h. It can still remove above 95% chlorophyll a after six consecutive recycles. Besides it has also shown excellent mechanical strength and elasticity, which can ensure its use in practical applications. The mechanisms of M. aeruginosa inactivation are attributed to •O2- and •OH generated by the ALFO hydrogel under visible light radiation. In addition, •O2- and •OH can further oxidative degrade and even mineralize the leaked algae organic matter, avoiding the recurrence of CyanoHABs. What's more, the ALFO hydrogel owns good photocatalytic degradation performance for microcystins-LR (MC-LR) with a 97% removal efficiency within 90 min. A possible photocatalytic degradation pathway of MC-LR was proposed through the identification of the intermediate products during the photocatalytic reaction, which confirmed the reduction of MC-LR toxicity. This work develops recyclable a self-floating ALFO hydrogel to simultaneously inactivate M. aeruginosa and degrade MC-LR, providing a prospective method for governing and controlling CyanoHABs in practical application.

Recyclable self-floating A-GUN-coated foam as effective visible-light-driven photocatalyst for inactivation of Microcystis aeruginosa.

In this work, a recyclable self-floating A-GUN-coated (Ag/AgCl@g-C3N4@UIO-66(NH2)-coated) foam was fabricated for effective inactivation of Microcystis aeruginosa (M. aeruginosa) under visible light. The floating photocatalyst was able to inactivate 98% of M. aeruginosa within 180 min under the visible-light irrigation, and the floating photocatalyst exhibited a stable performance in various conditions. Moreover, the inactivation efficiency can still maintain nearly 92% after five times recycle experiments, showing excellent photocatalytic stability. Furthermore, effects of A-GUN/SMF floating catalyst on the physiological properties, cellular organics, and algal functional groups of M. aeruginosa were studied. The floating photocatalyst can not only make full use of excellent photocatalytic activities of A-GUN nanocomposite, but also promote contact between catalyst and algae, and realize the effective recovery of the photocatalyst. Finally, possible photocatalytic inactivation mechanisms of algae were obtained, which provides references for removing cyanobacteria blooms in real water bodies.

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.

Efficient integration of plasmonic Ag/AgCl with perovskite-type LaFeO3: Enhanced visible-light photocatalytic activity for removal of harmful algae.

A novel plasmonic Ag/AgCl@LaFeO3 (ALFO) photocatalyst was successfully synthesized by a simple in-situ synthesis method with enhanced photocatalytic activity under visible light for harmful algal blooms (HABs) control. The structure, morphology, chemical states, optical and electrochemical properties of the photocatalyst were systematically investigated using a series of characterization methods. Compared with pure LaFeO3 and Ag/AgCl, ALFO-20% owned a higher light absorption capacity and lower electron-hole recombined rate. Therefore, ALFO-20% had higher photocatalytic activity with a near 100% removal rate of chlorophyll a within 150 min, whose kinetic constant was 15.36 and 9.61 times faster than those of LaFeO3 and Ag/AgCl. In addition, the changes of zeta potential, cell membrane permeability, cell morphology, organic matter, total soluble protein, photosynthetic system and antioxidant enzyme system in Microcystis aeruginosa (M. aeruginosa) were studied to explore the mechanism of M. aeruginosa photocatalytic inactivation. The results showed that ALFO-20% could change the permeability and morphology of the algae cell membrane, as well as destroy the photosynthesis system and antioxidant system of M. aeruginosa. What's more, ALFO could further degrade the organic matters flowed out after algae rupture and die, reducing the secondary pollution and avoiding the recurrence of HABs. Finally, the species of reactive oxygen species (ROS) (mainly •O2- and •OH) produced by ALFO were determined through quenching experiments, and a possible photocatalytic mechanism was proposed. Overall, ALFO can efficiently remove the harmful algae under the visible light, providing a promising method for controlling HABs.

Optimization of remedial nano-agent and its effect on dominant algal species succession in eutrophic water body.

A new method for algal community restructuring is proposed, where harmful algae growth is inhibited through the addition of remedial nano-agent, while probiotic algae growth is promoted or only affected indistinctively. In this paper, the inhibiting effects of five different nanomaterials on Microcystis aeruginosa (M. aeruginosa) and Cyclotella sp. were studied, and the optimal nanomaterial was served as algae-inhibition ingredient of the remedial agent. The effects of the remedial agent on algal growth and their physiological characteristics were investigated, and the restructuring of algal community in actual water samples was explored. The results indicated that the inhibition ratio of 10 mg/L nm-Cu2O/SiO2 on M. aeruginosa and Cyclotella sp. could reach 293.1% and 82.8% respectively, acting as the best candidate for algae-inhibiting ingredient. After adding the remedial nano-agent made with nm-Cu2O/SiO2, the content of chlorophyll a, protein, and polysaccharides of M. aeruginosa decreased sharply, while the physiological characteristics of Cyclotella sp. were not significantly affected. Besides, the total biomass and proportion of cyanobacteria dropped (P < 0.05), but the Bacillariophyta biomass increased significantly (P < 0.05). The uniformity index, Shannon-Wiener index, and richness index all increased significantly (P < 0.05). Meanwhile, the quality of actual water samples has been improved evidently (P < 0.001). Therefore, the prepared remedial nano-agent in this study can control the harmful algae bloom to a certain extent by restructuring the algal community in eutrophic water bodies.

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.

Occurrence and Fate of Steroid Estrogens in a Chinese Typical Concentrated Dairy Farm and Slurry Irrigated Soil.

Animal husbandry is the second largest source of steroid estrogen (SE) pollutants in the environment, and it is significant to investigate the occurrence and fate of SEs discharged from concentrated animal feeding operations. In this research, with a Chinese typical concentrated dairy farm as the object, the concentrations of SEs (E1, 17α-E2, 17ß-E2, E3, and E1-S3) in slurry, lagoon water, and slurry-irrigated soil samples in summer, autumn, and winter were determined. The total concentrations of SEs (mainly E1, 17α-E2, and 17ß-E2) in slurry were very high in the range of 263.1-2475.08 ng·L-1. In the lagoon water, the removal efficiencies of the aerobic tank could reach up to 89.53%, with significant fluctuation in different seasons. In the slurry-irrigated soil, the maximum concentrations of SEs in the topsoil and subsoil were 21.54 ng·g-1 to 6.82 g·g-1, respectively. Most of the SEs tended to transport downward and accumulate in the soil accompanied with the complex mutual conversion. Correlations and hierarchical clustering analysis showed a variety of intertransformation among SEs, and the concentrations of SEs were correlated with various physicochemical indexes, such as TN and NO3--N of the slurry, chemical oxygen demand of the lagoon water, and the heavy metals of soil. In addition, 17ß-estradiol equivalency assessment and risk quotients indicated that the slurry irrigation and discharge of the lagoon water would cause potential estrogenic risks to the environment. Consequently, reasonable slurry irrigation and lagoon water discharge are essential to efficiently control SE pollution in the environment.

Fabrication of heterostructured Ag/AgCl@g-C3N4@UIO-66(NH2) nanocomposite for efficient photocatalytic inactivation of Microcystis aeruginosa under visible light.

In this work, a novel Ag/AgCl@g-C3N4@UIO-66(NH2) heterojunction was constructed for photocatalytic inactivation of Microcystis aeruginosa (M. aeruginosa) under visible light. The photocatalyst was synthesized by a facile method and characterized by XRD, SEM, TEM, BET, XPS, FT-IR, UV-vis DRS, PL and EIS. The nanocomposite can not only provide lots of active sites, but also improve capacities to utilize visible-light energy and effectively transfer charge carriers, thus enhancing removal efficiencies of cyanobacteria (99.9% chlorophyll a was degraded within 180 min). Various factors in photodegradation of chlorophyll a were studied. Besides, changes on cellular morphologies, membrane permeability, physiological activities of M. aeruginosa during photocatalysis were investigated. Moreover, the cycle test indicated that Ag/AgCl@g-C3N4@UIO-66(NH2) exhibits excellent reusability and photocatalytic stability. Finally, a possible mechanism of M. aeruginosa inactivation was proposed. In a word, Ag/AgCl@g-C3N4@UIO-66(NH2) can efficiently inactivate cyanobacteria under visible light, thus providing useful references for further removal of harmful algae in real water bodies.

Occurrence and risk assessment of steroid estrogens in environmental water samples: A five-year worldwide perspective.

The ubiquitous occurrence of steroid estrogens (SEs) in the aquatic environment has raised global concern for their potential environmental impacts. This paper extensively compiled and reviewed the available occurrence data of SEs, namely estrone (E1), 17α-estradiol (17α-E2), 17ß-estradiol (17ß-E2), estriol (E3), and 17α-ethinyl estradiol (EE2), based on 145 published articles in different regions all over the world including 51 countries and regions during January 2015-March 2020. The data regarding SEs concentrations and estimated 17ß-estradiol equivalency (EEQ) values are then compared and analyzed in different environmental matrices, including natural water body, drinking and tap water, and wastewater treatment plants (WWTPs) effluent. The detection frequencies of E1, 17ß-E2, and E3 between the ranges of 53%-83% in natural water and WWTPs effluent, and the concentration of SEs varied considerably in different countries and regions. The applicability for EEQ estimation via multiplying relative effect potency (REPi) by chemical analytical data, as well as correlation between EEQbio and EEQcal was also discussed. The risk quotient (RQ) values were on the descending order of EE2 > 17ß-E2 > E1 > 17α-E2 > E3 in the great majority of investigations. Furthermore, E1, 17ß-E2, and EE2 exhibited high or medium risks in water environmental samples via optimized risk quotient (RQf) approach at the continental-scale. This overview provides the latest insights on the global occurrence and ecological impacts of SEs and may act as a supportive tool for future SEs investigation and monitoring.

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.

Feasibility and mechanism of enhanced 17ß-estradiol degradation by the nano Zero Valent Iron-citrate system.

17ß-Estradiol (17ß-E2) as a non-conventional pollutant with high damage, the effective removal of 17ß-E2 had been studied wildly. In recent years, nano materials application enabled the rapid removal of 17ß-E2. Nano zero valent iron (nZVI) as one of the most widely used nano materials could also be used to degrade 17ß-E2. But, the degradation performance of nZVI was limited by oxidation and aggregation. Therefore, this study explored the degradation mechanisms of 17ß-E2 by nZVI and the enhancement mechanisms of nZVI by citrate. Firstly, 17ß-E2 could be effectively degraded under acidic conditions without the addition of citrate. Citrate had protective effect on nZVI, so the degradation efficiency in neutral condition and degradation rate at all pH values of 17ß-E2 were enhanced greatly in nZVI-citrate system. 17ß-E2 degradation was mainly about group change and cleavage of ring A, as well as dominated by O2-▪ and OH∙ in the absence and presence of citrate. The formation of dimers and trimers proved the existence of laccase-like reaction during the 17ß-E2 degradation process by nZVI. In nZVI-citrate system, the laccase-like reaction was replaced by specific cross-coupling of 17ß-E2, E1, and citrate. Overall, the study proved that citrate could enhance the degradation of 17ß-E2 by nZVI.

Spatio-temporal distribution and transformation of 17α- and 17ß-estradiol in sterilized soil: A column experiment.

The environmental behaviors of steroid estrogens (SEs) associated with land irrigation and application are of critical concern worldwide. Understanding the spatio-temporal distribution and transformation process of these estrogenic compounds in soil is greatly significant. In this study, laboratory soil column experiments were conducted to investigate and explore the migration and abiotic transformation of 17α-estradiol (17α-E2) and 17ß-estradiol (17ß-E2) over spatial and time scales. Results indicated that the migration tendency of 17α-E2 and 17ß-E2 was similar. Discrepancies in transport for different SEs groups might be due to the competitive sorption and isomeric transformation in the binary-solute system. 17α-E2 and 17ß-E2 can also undergo the abiotic transformation during soil column transport. The soil with naturally abundant mineral substances (e.g., iron and manganese oxides) indicated that E2 isomers tended to mineral-promoted racemization, oxidation, reduction, and radical coupling reactions. Some possible transformation products (e.g., SE239, E2378, and SE dimer476) were identified and proposed in soil samples. Compared to the single compound tests, the estimated 17ß-estradiol equivalency (EEQ) values of E2 mixture were higher during SEs migration process.

Occurrence, sorption, and transformation of free and conjugated natural steroid estrogens in the environment.

Natural steroid estrogens (NSEs), including free estrogens (FEs) and conjugated estrogens (CEs), are of emerging concern globally among public and scientific community due to their recognized adverse effects on human and wildlife endocrine systems in recent years. In this review, the properties, occurrence, sorption process, and transformation pathways of NSEs are clarified in the environment. The work comprehensively summarizes the occurrence of both free and conjugated estrogens in different natural and built environments (e.g., river, WWTPs, CAFOs, soil, and sediment). The sorption process of NSEs can be impacted by organic compounds, colloids, composition of clay minerals, specific surface area (SSA), cation exchange capacity (CEC), and pH value. The degradation and transformation of free and conjugated estrogens in the environment primarily involves oxidation, reduction, deconjugation, and esterification reactions. Elaboration about the major, subordinate, and minor transformation pathways of both biotic and abiotic processes among NSEs is highlighted. The moiety types and binding sites also would affect deconjugation degree and preferential transformation pathways of CEs. Notably, some intermediate products of NSEs still remain estrogenic potency during transformation process; the elimination of total estrogenic activity needs to be addressed in further studies. The in-depth researches regarding the behavior of both free and conjugated estrogens are further required to tackle their contamination problem in the ecosystem. Graphical abstract ᅟ.