Algal Extracellular Organic Matter Induced Photochemical Oxidation of Mn(II) to Solid Mn Oxide: Role of Mn(III)-EOM Complex and Its Ability to Remove 17α-Ethinylestradiol.

Photosensitizer-mediated abiotic oxidation of Mn(II) can yield soluble reactive Mn(III) and solid Mn oxides. In eutrophic water systems, the ubiquitous algal extracellular organic matter (EOM) is a potential photosensitizer and may have a substantial impact on the oxidation of Mn(II). Herein, we focused on investigating the photochemical oxidation process from Mn(II) to solid Mn oxide driven by EOM. The results of irradiation experiments demonstrated that the generation of Mn(III) intermediate was crucial for the successful photo oxidization of Mn(II) to solid Mn oxide mediated by EOM. EOM can serve as both a photosensitizer and a ligand, facilitating the formation of the Mn(III)-EOM complex. The complex exhibited excellent efficiency in removing 17α-ethinylestradiol. Furthermore, the complex underwent decomposition as a result of reactions with reactive intermediates, forming a solid Mn oxide. The presence of nitrate can enhance the photochemical oxidation process, facilitating the conversion of Mn(II) to Mn(III) and then to solid Mn oxide. This study deepens our grasp of Mn(II) geochemical processes in eutrophic water and its impact on organic micropollutant fate.

Occurrence and cycle of dissolved iron mediated by humic acids resulting in continuous natural photodegradation of 17α-ethinylestradiol.

17α-ethinylestradiol (EE2), a synthetic endocrine-disrupting chemical, can degrade in natural waters where humic acids (HA) and dissolved iron (DFe) are present. The iron is mostly bound in Fe(III)-HA complexes, the formation process of Fe(III)-HA complexes and their effect on EE2 degradation were explored in laboratory experiments. The mechanism of ferrihydrite facilitated by HA was explored with results indicating that HA facilitated the dissolution of ferrihydrite and the generation of Fe(III)-HA complexes with the stable chemical bonds such as C-O, CO in neutral, alkaline media with a suitable Fe/C ratio. 1O2, •OH, and 3HA* were all found to be important in the photodegradation of EE2 mediated by Fe(III)-HA complexes. Fe(III)-HA complexes could produce Fe(II) and hydrogen peroxide (H2O2) to create conditions suitable for photo-Fenton reactions at neutral pH. HA helped to maintain higher dissolved iron concentrations and alter the Fe(III)/Fe(II) cycling. The natural EE2 photodegradation pathway elucidated here provides a theoretical foundation for investigating the natural transformation of other trace organic contaminants in aquatic environments.

Dissolved organic matter accelerates microbial degradation of 17 alpha-ethinylestradiol in the presence of iron mineral.

Dissolved organic matter (DOM) and iron minerals widely existing in the natural aquatic environment can mediate the migration and transformation of organic pollutants. However, the mechanism of interaction between DOM and iron minerals in the microbial degradation of pollutants deserves further investigation. In this study, the mechanism of 17 alpha-ethinylestradiol (EE2) biodegradation mediated by humic acid (HA) and three kinds of iron minerals (goethite, magnetite, and pyrite) was investigated. The results found that HA and iron minerals significantly accelerated the biodegradation process of EE2, and the highest degradation efficiency of EE2 (48%) was observed in the HA-mediated microbial system with pyrite under aerobic conditions. Furthermore, it had been demonstrated that hydroxyl radicals (HO•) was the main active substance responsible for the microbial degradation of EE2. HO• is primarily generated through the reaction between hydrogen peroxide secreted by microorganisms and Fe(II), with aerobic conditions being more conducive. The presence of iron minerals and HA could change the microbial communities in the EE2 biodegradation system. These findings provide new information for exploring the migration and transformation of pollutants by microorganisms in iron-rich environments.

Sunlight-induced degradation of COVID-19 antivirals arbidol in natural aquatic environments: Mechanisms, pathways and toxicity.

Insights into COVID-19 antivirals' environmental fate and ecological risk are urgently required due to their increasing concentrations in aquatic environments, which have rarely been studied. Herein, we first investigated the photochemical transformation and the resulting alterations in toxicity of arbidol, an antiviral drug with relatively higher toxicity. The photolysis of arbidol was rapid with a rate constant of 0.106 min-1 due to its superior ultraviolet light absorption, in which the direct photolysis was predominated with a contribution of 91.5%. Despite its substantial photolysis, only 14.45% of arbidol was mineralized after 100 min, implying that arbidol and its products might have a long-term impact on aquatic environment. It was inferred that arbidol was photolyzed mainly via the loss of thiophenol, bromine, and alkylamine, based on twelve photolytic products identified. Notably, the experimental results demonstrated that the photolysis process increased the acute toxicity of arbidol, and the toxicity prediction indicated that the ecotoxicity of two photolytic products was very high with LC50 values below 0.1 mg/L. Due to the co-effect of multiple constituents, the photolytic rate observed in wastewater treatment plant effluent and in river water was comparable to that in ultra-pure water, while it was slightly enhanced in lake water. The presence of dissolved organic matter suppressed arbidol photolysis, while NO3- exhibited a promotion effect. These results would be of great significance to assess the fate and risk of COVID-19 antivirals in natural aquatic environments.

Variation in photochemical properties of dissolved black carbon during bio-transformation and iron mineral fractionation process.

The excellent photochemical properties of dissolved black carbon (DBC) have been proven to be a significant contributor to the removal of organic pollutants in environment. However, the photochemical properties of DBC will inevitably be changed during biotic and abiotic processes. Herein, the structures and compositions of DBC during bio-transformation and goethite adsorption processes were comprehensively studied, and their corresponding photochemical properties were also evaluated. Bio-transformed DBC (B-DBC) contained more aromatic, high molecular weight, and phenolic substances compared with pristine DBC (P-DBC). The photodegradation of 17α-ethynylestradiol (EE2) was significantly promoted by B-DBC because of its superior capacity for producing 3DBC*. Moreover, the subsequent goethite fractionation selectively reduced the parts of components with high aromaticity and carboxylic functional groups in B-DBC. The interaction between B-DBC and goethite resulted in the release of Fe2+ into goethite-fractionated DBC (G-DBC), which induced the photodegradation mechanism of EE2 shifting from a single-electron transfer driven by 3DBC⁎ to the oxidation of •OH. This study provides valuable insights into the changes in photochemical behavior of DBC resulting from biotic or abiotic processes, and enhances our understanding of the role of DBC in the fate of organic pollutants.

The photolytic behavior of COVID-19 antivirals ribavirin in natural waters and the increased environmental risk.

Increasing drug residues in aquatic environments have been caused by the abuse of antivirals since the global spread of the COVID-19 epidemic, whereas research on the photolytic mechanism, pathways and toxicity of these drugs is limited. The concentration of COVID-19 antivirals ribavirin in rivers has been reported to increase after the epidemic. Its photolytic behavior and environmental risk in actual waters such as wastewater treatment plant (WWTP) effluent, river water and lake water were first investigated in this study. Direct photolysis of ribavirin in these media was limited, but indirect photolysis was promoted in WWTP effluent and lake water by dissolved organic matter and NO3-. Identification of photolytic intermediates suggested that ribavirin was photolyzed mainly via C-N bond cleavage, splitting of the furan ring and oxidation of the hydroxyl group. Notably, the acute toxicity was increased after ribavirin photolysis owing to the higher toxicity of most of the products. Additionally, the overall toxicity was greater when ARB photolysis in WWTP effluent and lake water. These findings emphasize the necessity to concern about the toxicity of ribavirin transformation in natural waters, as well as to limit its usage and discharge.

The disinfectant residues promote the leaching of water contaminants from plastic pipe particles.

Disinfection treatment is an indispensable water purification process, but it can leave trace concentrations of disinfectant in the purified water. Disinfectants oxidation can age plastic pipes and release hazardous microplastics and chemicals into drinking water. Lengths of commercially-available unplasticized polyvinyl chloride and polypropylene random copolymer water pipe were ground into particles and exposed to micro-molar concentrations of ClO2, NaClO, trichloroisocyanuric acid, or O3 for up to 75 days. The disinfectants aged the plastic and changed its surface morphology and functional groups. Meanwhile, disinfectants could significantly promote the release of organic matter from plastic pipes into the water. ClO2 generated the highest concentrations of organic matter in the leachates from both plastics. Plasticizers, antioxidants and low molecular weight organic matter were detected in all of the leachates. Leachate samples inhibited the proliferation of CT26 mouse colon cancer and induced oxidative stress in the cells. Even trace concentrations of residual disinfectant can constitute a drinking water risk.

The efficient treatment of mature landfill leachate using tower bipolar electrode flocculation-oxidation combined with electrochemical biofilm reactors.

Mature landfill leachate contains high concentrations of organic and inorganic compounds that inhibit the performance of conventional biological treatment. Nowadays, few single treatment techniques could fulfill the requirements of cleaning mature landfill leachate. In this study, a tower bipolar electrode flocculation-oxidation (BEF-O) reactor and an electrochemical biofilm reactor (EBR) combine device was constructed to effectively treat mature landfill leachate. And the removal efficiency and mechanism of various pollutants using the BEF-O reactor were investigated. The BEF-O system with the current density of 100 mA/cm2 shows excellent treatment efficiency, which can roundly remove most pollutants (NH4+-N, COD and heavy metals, etc.), and increase the bioavailability of the effluent to facilitate subsequent EBR treatment. Benefiting from the metabolic stimulation and population selection effect of electric current on microorganisms, EBR has a denser biofilm, stronger anti-pollution load capacity, superior, and stable pollution treatment efficiency. More importantly, the combined device can reduce the concentrations of COD and NH4+-N from 6410 to 338 mg/L and 4065 to 4 mg/L, respectively, and has an economical energy consumption of 32.02 kWh/(kg COD) and 54.04 kWh/ (kg NH4+-N). To summarize, this research could provide an innovative and industrial application prospect technology for the mature landfill leachate treatment.

The desorption mechanism of dissolved organic matter on pollutants and the change of biodiversity during sediment dredging.

Sediment dredging is an effective means to control the endogenous pollution of lakes, which could significantly change the concentration and composition of organic matter, especially dissolved organic matter (DOM) in the lake. DOM is particularly important for the release of endogenous pollutants, which will inevitably bring an impact on aquatic biodiversity. Nevertheless, in recent research little attention has been paid to the desorption mechanism of DOM on pollutants and the change of biodiversity during dredging. This study investigated the physicochemical properties of DOM in the sediment by taking a sediment dredging project in Dianchi Lake in China for example. The correlations of DOM properties with the desorption behavior of nitrogen (N), phosphorus (P), cadmium (Cd), lead (Pb) and the biodiversity of aquatic organisms were analyzed. The results show that the aromaticity and humification of DOM were improved after dredging, and the high molecular weight DOM was degraded into low molecular weight substance. The desorption amount of N, P and heavy metals (Cd, Pb) were decreased as the pH values increased. Moreover, NH4+-N promoted the release of Pb2+ from DOM, while the release of PO43--P was inhibited. Correlation analysis shows that the physicochemical properties of DOM exactly affected the release of N, P, Cd and Pb. It was easier to desorb pollutants with low aromaticity and humification of DOM, leading to a decrease in the diversity of aquatic organisms. This study identified the desorption mechanism of endogenous pollutants in DOM and the ecological risk to aquatic organisms, providing a theoretical basis for the prevention and control of water pollution.

Adsorption and photochemical capacity on 17α-ethinylestradiol by char produced in the thermo treatment process of plastic waste.

Plastic is a major component of solid waste. It is often thermally treated, generating microplastics and plastic-char which end up as landfill. This study investigated the potential of plastic-char for treating persistent organic pollutants of aqueous media using 17α-ethinylestradiol (EE2) as a target contaminant. The adsorption and photodegradation capacity of plastic-char were investigated, and the adsorption isotherms revealed that EE2 adsorption on char is heterogeneous and multilayered. The presence of Fe was found to greatly enhance EE2 adsorption rate and capacity as well as photochemical degradation ability of plastic-char. Quenching experiments proved that electron transfer between triplet states of plastic-char and Fe(III) and the production of H2O2 were the rate-limited steps in the generation of reactive species. Hydroxyl radical and holes were found to be the predominant reactive species contributing to the EE2 photodegradation. This study not only elucidated the possible environmental behavior of plastic-char discharged as bottom ash in the natural transformation of persistent organic pollutants, but also suggested that water treatment may offer a use for some of the enormous volume of plastic waste now being generated worldwide.

The photodegradation of 17 alpha-ethinylestradiol in water containing iron and dissolved organic matter.

17 alpha-ethinylestradiol (EE2) in natural waters can seriously harm ecosystems and human health. Dissolved organic matter (DOM) and iron minerals are ubiquitous in natural waters, and they can shorten the half-life of EE2 in the natural environment. The interaction between dissolved organics and iron affects pollutants' transformation pathways. The mechanism of EE2's adsorption on hematite, magnetite and pyrite was studied. A photo-Fenton system was constructed in which humic acid (HA) and iron minerals degraded EE2 under simulated natural light conditions. Pyrite showed the best adsorption and degradation in acidic conditions (52%) for 5 h. Hydroxyl radical was found to be the main active substance in the photodegradation. The degradation products of EE2 were identified and possible degradation pathways were inferred. These results can contribute to the understanding of the transformation pathways of persistent organic pollutants in natural waters.

Double-dose responses of Scenedesmus capricornus microalgae exposed to humic acid.

Dissolved organic matter (DOM) has been found to attenuate the ecotoxicity of various environmental pollutants, but research on its own toxic effects in aquatic ecosystems has been very limited. Herein, the toxic effects of humic acid (HA), a represent DOM typically found in natural waters, on the freshwater alga Scenedesmus capricornus were investigated. As result, HA exerted a double-dose effect on the growth of Scenedesmus capricornus. At HA concentrations below 2.0 mgC/L, the growth of Scenedesmus capricornus was slightly promoted, as was the synthesis of chlorophyll and macromolecules in the algae. Moreover, S. capricornus can maintain its growth by secreting fulvic acid as a nutrient carbon source. However, the growth of Scenedesmus capricornus was significantly inhibited when HA was beyond 2.0 mgC/L. The main mechanisms of humic acid's toxicity were membrane damage and oxidative stress. Particularly, when the oxidative stress exceeds the algae's carrying capacity, the synthesis of EPS is greatly inhibited and HA damage results. Taken together, DOM may have both positive and negative effects on aquatic ecosystems.

Simultaneous changes of exogenous dissolved organic matter treated by ozonation in properties and interaction behavior with sulfonamides.

Effluent is often treated with ozone before being discharged into a natural water environment. This process will change the interaction between effluent organic matter and pollutants in aquatic environment. The impact of ozonation on complexation between dissolved organic matter in such wastewater and sulfadimidine often found in natural water was studied in laboratory experiments using four types of real wastewater. Ozonation was found to decrease the proportion of organic matter with a molecular weight greater than 5 kDa as well as protein-like, fulvic-like and humic-like components, but except the proportion of hydrophilic components. The aromaticity of the dissolved organic matter was also reduced after ozonation. The complexation of tryptophan and tyrosine with sulfadimidine mainly depends on their hydrophobicity and large molecular weight. Ozonation of fulvic and humic acid tends to produce small and medium molecular weight hydrophilics. The complexation of humic and fulvic acids with sulfadimidine was enhanced by ozonation. Dissolved organic matter, with or without oxidation, were found to weaken sulfadimidine's inhibition of microbial growth, especially for Aeromonas and Acinetobacter species. This finding will expand our understanding about the impact of advanced treatment processes on the dissolved organic matters' properties in effluent.

Modified humic acids mediate efficient mineralization in a photo-bio-electro-Fenton process.

Humic acids (HA) are common mediators in redox reactions in the aquatic environment. The structures and properties of HA are greatly influenced by environmental factors such as external electrons. In this study, qualitative changes in electron-modified HA and the underlying mechanisms were reported, which not only contribute to understanding the fate of HA and their impact on organic pollutants, but could facilitate their potential use for water purification. The photochemical activity and electron-donating capacity of HA were improved due to the increase of phenolic and carboxyl components via the reduction modification by electrons, creating a novel and efficient photo-bio-electro-Fenton system mediated by HA under neutral conditions without the use of hydrogen peroxide (H2O2). The in-situ continuous production of H2O2 ensured an adequate supply of hydroxyl radicals in this coupled system, achieving mineralization (92%) of HA and 17α-ethinylestradiol (EE2), a common synthetic estrogen with high estrogenic potency. Two degradation pathways with five degradation intermediates of EE2 were identified in our study. Effluents from the coupled system showed decreased endocrine-disrupting activity. Our findings demonstrated a new approach for the in-situ modification and potential use of HA for water treatment and particularly the concurrent degradation of HA and organic pollutants through a photo-bioelectrochemical system mediated by HA.

Biochar enhanced microbial degradation of 17ß-estradiol.

Steroid estrogens (SEs), especially 17ß-estradiol (E2), can be a serious threat to the health of organisms. The removal of E2 from the natural environment is mainly carried out by microbial degradation partly mediated by biochar, which contains quinone structures. In this study, reed straw biochar samples made at four different heat treatment temperatures (HTTs) were used to mediate E2 microbial degradation by Shewanella oneidensis MR-1. The removal efficiency of E2 (95%) was highest in the presence of HTT - 500 °C biochar under anaerobic conditions after 120 h of microbial degradation. The effect of biochar on promoting microbial degradation was far more superior under anaerobic conditions than under aerobic conditions. The redox-activity and types of surface functional groups of biochar reveal that biochar can accept electrons generated by microorganisms in a timely manner. This mechanism promotes the metabolic process of cells and microbial degradation of E2 (exponential increase). Biochar particles rather than biochar-derived water-soluble organic compounds are responsible for this stimulating effect. These results highlight the impact that biochar has on microbial degradation of trace pollutants in a natural environment.

Microbially reduced humic acid promotes the anaerobic photodegradation of 17α--ethinylestradiol.

Photolysis and microbial activity are relatively obvious in shallow, eutrophic waters with low dissolved oxygen content. Ubiquitous humic acid (HA) can act as electron acceptor and be reduced by bacterial under such conditions, and the reduced form of humic acid (RHA) plays an important role in the photolysis contaminants. In this study, anaerobic 17α-ethinylestradiol (EE2) photodegradation was performed along with biodegradation by Shewanella putrefaciens mediated by HA. The mechanism of such coupled photolysis and biodegradation of EE2 was thus elucidated. The removal rate in such coupled degradation in the presence of 10 mgC L-1 of HA at pH 8.0 was greater than that of either photolysis or biodegradation alone. HA which had been reduced in a double-chamber microbial fuel cell showed better promotion to EE2 photodegradation than fresh HA. Reactive species scavenging experiments indicated that hydroxyl radical and excited triplet states of HA were primary contributors to EE2 photodegradation in anaerobic conditions. More of them were produced from RHA than from pristine HA. Besides, the degraded EE2 solutions inhibited the proliferation of MCF-7 human cancer Cells. These findings improve our understanding of the environmental transformation of EE2 in the shallow, anoxic waters.

The microbial transformation of 17ß­estradiol in an anaerobic aqueous environment is mediated by changes in the biological properties of natural dissolved organic matter.

Dissolved organic matter (DOM) is shown to act as an electron shuttle mediator which enhances the microbial degradation of steroid estrogens in natural water. Batch studies were conducted with 17ß­estradiol (E2), quinone-reducing bacteria, DOM, and Fe(III) as a terminal electron acceptor. The results show that anthraquinone­2­disulfonate (AQS) approximately doubles the microbial degradation of E2 by DOM alone. The effect decreases sharply at AQS concentrations above 1.0mmol·L-1. Over three oxidation-reduction cycles, the electron-shuttling ability of AQS and the E2 biodegradation rate decreased step by step. Changes in the biological properties of the dissolved organic matter increased its aromaticity, its quinone content, and its fulvic-like fluorescence while significantly improving the electron transfer between DOM and the microbes, which made the degradation more effective. This explains why steroid estrogens do not accumulate in natural aqueous environments. Moreover, the estrogenic activity of steroid estrogens is inhibited at low concentrations through the activity of DOM.

Coupling electrochemical and biological methods for 17α-ethinylestradiol removal from water by different microorganisms.

17α-ethynylestradiol (EE2) has become a growing concern due to its wide detection and high estrogenic potency. However, biodegradation of EE2 with individual microorganisms demonstrated poor degradation efficiency ranging from 10.3% to 45.8% in 120h. Now, a system combining electrochemical with biological degradation was tested for its ability to remove EE2 from aqueous solution. EE2 removal is promoted at high dissolved oxygen concentrations and low pH when electrochemical methods alone are employed. Coupling electrochemical methods with anaerobic bacteria can improve the EE2 removal after 90min to as much as 81.9% with a reaction rate constant of 0.0195min-1. An electric current of 100mA at pH5.5 inhibits the growth of most microbial species, but Shewanella and Aeromonas survive well. They can enhance the efficiency of direct electron transfer efficiency between the bacteria and the electrodes, promoting EE2 degradation. This study provided a theoretical basis for the future applicability of bioelectrochemical technology to remove steroids from waste water.