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High energy consumption has seriously hindered the development of Fenton-like reactions for the removal of refractory organic pollutants in water. To solve this problem, we designed a novel Fenton-like catalyst (Cu-PAN 3 ) by coprecipitation and carbon thermal reduction. The catalyst exhibits excellent Fenton-like catalytic activity and stability for the degradation of various pollutants with low H 2 O 2 consumption. The experimental results indicate that the dual reaction centers (DRCs) are composed of Cu-N-C and Cu-O-C bridges between copper and graphene-like carbon, which form electron-poor/rich centers on the catalyst surface. H 2 O 2 is mainly reduced at electron-rich Cu centers to free radicals for pollutant degradation. Meanwhile, pollutants can be oxidized by donating electrons to the electron-poor C centers of the catalyst, which inhibits the ineffective decomposition of H 2 O 2 at the electron-poor centers. This therefore significantly reduces the consumption of H 2 O 2 and reduces energy consumption., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Antibiotics release into the water environment through sewage discharge is a significant environmental concern. In the present study, we investigated the removal of ciprofloxacin (CIP) in simulated sewage by biological aeration filter (BAF) equipped with Fe 3 O 4 -modified zeolite (Fe 3 O 4 @ZF). Fe 3 O 4 @ZF were prepared with impregnation method, and the Fe 3 O 4 particles were successfully deposited on the surface of ZF in an amorphous form according to the results of XPS and XRD analysis. The modification also increased the specific surface area (from 16.22 m²/g to 22 m²/g) and pore volume (from 0.0047 cm³/g to 0.0063 cm³/g), improving the adsorption efficiency of antibiotics. Fe 3 O 4 modified ZF improved the treatment performance significantly, and the removal efficiency of CIP in BAF-Fe 3 O 4 @ZF was 79%±2.4%. At 10ml/L CIP, the BAF-Fe 3 O 4 @ZF reduced the relative abundances of antibiotics resistance genes (ARGs) int, mexA, qnrB and qnrS in the effluent by 57.16%, 39.59%, 60.22%, and 20.25%, respectively, which effectively mitigate the dissemination risk of ARGs. The modification of ZF increased CIP-degrading bacteria abundance, such as Rhizobium and Deinococcus-Thermus , and doubled bacterial ATP activity, promoting CIP degradation. This study offers a viable, efficient method to enhance antibiotic treatment and prevent leakage via sewage discharge ., Competing Interests: The authors declare there is no conflict., (© 2024 The Authors This is an Open Access article distributed under the terms of the Creative Commons Attribution Licence (CC BY 4.0), which permits copying, adaptation and redistribution, provided the original work is properly cited (http://creativecommons.org/licenses/by/4.0/).)

Microplastics (MPs) migrate by adsorbing heavy metals in aquatic environments and act as their carriers. However, the aging mechanisms of MPs in the environment and the interactions between MPs and heavy metals in aquatic environments require further study. In this study, two kinds of materials, polyamide (PA) and polylactic acid (PLA) were used as target MPs, and the effects of UV irradiation on the physical and chemical properties of the MPs and the adsorption behavior of Cu(II) were investigated. The results showed that after UV irradiation, pits, folds and pores appeared on the surface of aged MPs, the specific surface area (SSA) increased, the content of oxygen-containing functional groups increased, and the crystallinity decreased. These changes enhanced the adsorption capacity of aged MPs for Cu(II) pollutants. The adsorption behavior of the PA and PLA MPs for Cu(II) conformed to the pseudo-second-order model and Langmuir isotherm model, indicating that the monolayer chemical adsorption was dominant. The maximum amounts of aged PA and PLA reached 1.415 and 1.398 mg/g, respectively, which were 1.59 and 1.76 times of virgin MPs, respectively. The effects of pH and salinity on the adsorption of Cu(II) by the MPs were significant. Moreover, factors such as pH, salinity and dosage had significant effects on the adsorption of Cu(II) by MPs. Oxidative complexation between the oxygen-containing groups of the MPs and Cu(II) is an important adsorption mechanism. These findings reveal that the UV irradiation aging of MPs can enhance the adsorption of Cu(II) and increase their role as pollutant carriers, which is crucial for assessing the ecological risk of MPs and heavy metals coexisting in aquatic environments., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The effects of trace sulfadiazine (SDZ) and cast-iron corrosion scales on the disinfection by-product (DBP) formation in drinking water distribution systems (DWDSs) were investigated. The results show that under the synergistic effect of trace SDZ (10 μg/L) and magnetite (Fe 3 O 4 ), higher DBP concentration occurred in the bulk water with the transmission and distribution of the drinking water. Microbial metabolism-related substances, one of the important DBP precursors, increased under the SDZ/Fe 3 O 4 condition. It was found that Fe 3 O 4 induced a faster microbial extracellular electron transport (EET) pathway, resulting in a higher microbial regrowth activity. On the other hand, the rate of chlorine consumption was quite high, and the enhanced microbial EET based on Fe 3 O 4 eliminated the need for microorganisms to secrete excessive extracellular polymeric substances (EPS). More importantly, EPS could be continuously secreted due to the higher microbial activity. Finally, high reactivity between EPS and chlorine disinfectant resulted in the continuous formation of DBPs, higher chlorine consumption, and lower EPS content. Therefore, more attention should be paid to the trace antibiotics polluted water sources and cast-iron corrosion scale composition in the future. This study reveals the synergistic effects of trace antibiotics and corrosion scales on the DBP formation in DWDSs, which has important theoretical significance for the DBP control of tap water., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The biofilm stress response of biological activated carbon (BAC) was investigated under prolonged exposure to sulfadiazine and 2,4-Dichlorophenoxyacetic acid, simulating complex emerging organic contaminants (EOCs) that are mainly involved in the formation of nitrogenous disinfection byproducts (N-DBPs) and antibiotic resistance genes (ARGs). Under trace complex EOCs condition (2 µg/L), N-DBP precursors and abundance of ARGs increased significantly in BAC effluent. The total formation potential of haloacetonitriles (HANs) and halonitromethanes (HNMs) was 751.47 ± 2.98 ng/L, which was much higher than the control group (440.67 ± 13.38 ng/L without EOCs). Similarly, the relative abundance of ARGs was more than twice that in the control group. The complex EOCs induce excessive extracellular polymeric substance secretion (EPS), thereby causing more N-DBP precursors and stronger horizontal gene transfer. Metagenome analysis revealed that functional amino acid and protein biosynthesis genes were overexpressed compared to the control group, causing more EPS to be secreted into the external environment. Complex EOCs promote Cobetia, Clostridium, and Streptomyces dominance, contributing to the production of N-DBP precursors and ARGs. For the first time, in addition to the direct hazards of the EOCs, this study successfully revealed the indirect water quality risks of complex EOCs from the microbial stress response during BAC treatment. Synergistic regulation of EOCs and microorganisms is important for tap water security., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The use of catalyst materials to mediate the enhancement of microbial degradation in wastewater is a new economic and energy saving breakthrough in water treatment technology. In this study, γ-Al 2 O 3 , which is commonly used as catalyst/carrier, is used as biological filler to treat kitchen-oil wastewater with low biodegradability, and the COD removal rate is about 50 %. It is found that the complexation of cationic vacancies on Al 2 O 3 surface with extracellular polymeric substance (EPS) secreted by microorganisms in wastewater lead to the polarization of electron distribution on biofilm. The efficient degrading bacteria are enriched on reaction interface and obtain electrons to maintain electron dynamic balance by enhancing the transmembrane metabolism of pollutants. The aluminum vacancies on Al 2 O 3 surface accelerate the microbial degradation of pollutants. The cationic vacancies in the structure of catalyst accelerate the acquisition of exogenous electrons by microorganisms without the addition of external energy, which provides a new idea for catalytic fillers to enhance wastewater degradation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

The adsorption of pollutants can not only promote the direct surface reaction, but also modify the catalyst itself to improve its photoelectric characteristics, which is rarely studied for water treatment with inorganic photocatalyst. A highly crystalline BiOBr (c-BiOBr) was synthesized by a two-step preparation process. Owing to the calcination, the highly crystalline enhanced the interface interaction between pollutant and c-BiOBr. The complex of organic pollutant and [Bi 2 O 2 ] 2+ could promote the active electron transfer from the adsorbed pollutant to c-BiOBr for the direct pollutant degradation by holes (h + ). Moreover, the pollutant adsorption actually modified c-BiOBr and promoted more unpaired electrons, which would coupling with the photoexcitation to promote generate more O 2 •- . The molecular modification effect derived from pollutant adsorption significantly improved the removal of pollutants. This work strongly deepens the understanding of the molecular modification effect from the pollutant adsorption and develops a novel and efficient approach for water treatment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influencethe work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

The stable structure and toxic effect of refractory organic pollutants in wastewater lead to the problem of high energy consumption in water treatment technology. Herein, we propose a synergistic purification of refractory wastewater driven by microorganisms and surface microelectric fields (SMEF) over a dual-reaction-center (DRC) catalyst HCLL-S8-M prepared by an in situ growth method of carbon nitride on the Cu-Al 2 O 3 surface. Characterization techniques demonstrate the successful construction of SMEF with strong electrostatic force over HCLL-S8-M based on cation-π interactions between metal copper ions and carbon nitride rings. With the catalyst as the core filler, an innovative fixed bed bioreactor is constructed to purify the actual kitchen-oil wastewater. The removal efficiency of the wastewater even with a very low biodegradability (BOD 5 /COD = 0.33) can reach 60% after passing through this bioreactor. An innovative reaction mechanism is revealed for the first time that under the condition of a small amount of biodegradable organic matter, the SMEF induces the enrichment of electric active microorganisms (Desulfobulbus and Geobacter) in the wastewater, accelerates the interspecies electron transfer of intertrophic metabolism with the biodegradable bacteria through the extracellular electron transfer mechanism such as cytochrome C and self-secreted electron shuttle. The electrons of the refractory organic pollutants adsorbed on the surface of the catalyst are delocalized by the SMEF, which can be directly utilized by microorganisms through EPS conduction. The SMEF generated by electron polarization can maximize the utilization of pollutants and microorganisms in wastewater and further enhance degradation without adding any external energy, which is of great significance to the development of water self-purification technology., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Removing micropollutants in real water is a scientific challenge due to primary dissolved organic carbon (DOC) and high energy consumption of current technologies. Herein, we develop a self-purification process for the preferential destruction of various micropollutants in municipal wastewater, raw drinking water, and ultrapure water with humic acid (HA) driven by the surface microelectronic field of Fe 0 -Fe y C z /Fe x -GZIF-8-rGO without any additional input. It was verified that a strongly polar complex consisting of an electron-rich HA/DOC area and an electron-poor micropollutant area was formed between HA/DOC and micropollutants, promoting more electrons of micropollutants in the adsorbed complex to delocalizing to electron-rich Fe species area and be trapped by O 2 , which resulted in their surface cleavage and hydrolyzation preferentially. The higher micropollutant degradation efficiency observed in real wastewaters was due to the greater complex polarity of DOC. Moreover, the electron transfer process ensured the stability of the surface microelectronic field and continuous water purification. Our findings provide a new insight into low-energy combined-micropollution water treatment.

The main function of quartz sand in drinking water treatment has been to remove turbidity, while the microbial effect of its solid-liquid interface has been ignored. In order to solve the limitations of control of the disinfection by-products (DBPs) and opportunistic pathogens (OPs) in common quartz sand, the common quartz sand was modified to iron sand. The maximum DBPs formation potential of typical nitrogenous disinfection by-products (N-DBPs) and carbonaceous disinfection by-products was determined using gas chromatography-ECD. Compared with those of sand, the inhibition effects of halonitromethanes, haloacetamides, and haloacetonitriles by the Fe-sand were increased by 51.51%, 43.66%, and 90.6%, respectively. In addition, the gene copy numbers of Hartmanella vermiformis, Legionella spp., Mycobacterium spp., M. avium , and Naegleria spp. were detected via quantitative qPCR, and the results indicated that the Fe-sand did have a similar significant inhibitory effect on OPs. The Fe-sand had limited ability to enhance the removal of NOM. However, the Fe-sand effectively inhibited the continuous contribution of biofilm to N-DBPs and opportunistic pathogens. The distribution of biofilms on the surface of the Fe-sand filter media was uniform, not likely to fall off, and more stable; however, the suspended biofilms in the effluent were more difficult to aggregate. In addition, the α -helix of the secondary structure in the extracellular protein disappeared in the effluent of the Fe-sand. Therefore, the whole suspended biofilm was easily penetrated by chlorine. The Fe-sand solid-liquid interface did significantly change the microbial community structure and suspended biofilm characteristics, which provides a new concept to ensure the safety of drinking water quality and plays a good theoretical supporting role in the improvement and transformation of the existing process in drinking water treatment plants.

Change in water quality was investigated with laboratory-scale ozone-biological activated carbon filters using copper-modified granular activated carbon (Cu/GAC) and unmodified granular activated carbon (GAC). In the first seven days of the experimental period, Cu/GAC removed organic matter more efficiently owing to its enhanced adsorption capacity. As the running time increased, the amount of disinfection by-products (DBPs), dissolved organic carbon, and extracellular polymeric substances (EPS) increased sharply in the effluent of the Cu/GAC filter (CCW). More importantly, the EPS suspended in the CCW exhibited weaker flocculating efficiency and hydrophobicity, causing more active chemical reactions between chlorine and EPS substances. The copper species significantly limited the microbial biomass (0.01 nmol/L adenosine triphosphate) but stimulated the secretion of significant amounts of EPS by microorganisms for self-protection. Furthermore, the microbial community in the bulk water was successfully shaped by Cu/GAC, resulting in a continuous supply of EPS-derived DBP precursors and a sharp rise in chlorine consumption in the downstream drinking water distribution. Therefore, use of modified GAC materials, similar to Cu/GAC, as carrier materials for biological activated carbon (BAC) treatment remains controversial, despite enhanced pollutant adsorption capacity. This is the first study to reveal the mechanism of BAC-modified materials for water quality stability. The study potentially contributes to a comprehensive understanding of the effects of biofilm transformation and microbial community succession on drinking water quality. These results showed that tap water safety risks could be reduced by improving BAC pretreatment in drinking water treatment plants., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The effects of biological activated carbon treatment using Fe 2 O 3 modified coconut shell-based activated carbon (Fe/CAC) were investigated on the occurrence of opportunistic pathogens (OPs) and formation of disinfection by-products (DBPs) in simulated drinking water distribution systems (DWDSs) with unmodified CAC as a reference. In the effluent of annular reactor (AR) with Fe/CAC, the OPs growth and DBPs formation were inhibited greatly. Based on the differential pulse voltammetry and dehydrogenase activity tests, it was verified that extracellular electron transfer was enhanced in the attached biofilms of Fe/CAC, hence improving the microbial metabolic activity and biological removal of organic matter especially DBPs precursors. Meanwhile, the extracellular polymeric substances (EPS) on the surface of Fe/CAC exhibited stronger viscosity, higher flocculating efficiency and better mechanical stability, avoiding bacteria or small-scale biofilms falling off into the water. Consequently, the microbial biomass and EPS substances amount decreased markedly in the effluent of Fe/CAC filter. More importantly, Fe/CAC did significantly enhance the shaping role on microbial community of downstream DWDSs, continuously excluding OPs advantage and inhibiting EPS production. The weakening of EPS in DWDSs resulted in decrease of microbial chlorine-resistance ability and EPS-derived DBPs precursors supply. Therefore, the deterioration of water quality in DWDSs was inhibited greatly, sustainably maintaining the safety of tap water. Our findings indicated that optimizing biological activated carbon treatment by interface modification is a promising method for improving water quality in DWDSs., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

In this study, bacterial mercury (Hg) methylation was investigated under the influence of red-tide algae of Skeletonema costatum (S. costatum). The distribution and speciation of total mercury (THg) and methylmercury (MeHg) were profiled by employing Geobacter metallireducens (G. metallireducens GS-15) as the methylating bacteria. G. metallireducens GS-15 showed different capabilities in methylating different inorganic forms of Hg(II) (HgCl 2 ) and Hg(II)-Algae (HgCl 2 captured by S. costatum) to MeHg. In the absence of S. costatum, a maximum methylation efficiency of 4.31 ± 0.47% was achieved with Hg(II) of 1-100 μg L -1 , while accelerated MeHg formation rate was detected at a higher initial Hg(II) concentration. In the presence of S. costatum, there were distinct changes in the distribution of THg and MeHg by altering the bioavailability of Hg(II) and Hg(II)-Algae. A larger proportion of THg tended to be retained by a higher algal biomass, resulting in decreased methylation efficiencies. The methylation efficiency of Hg(II) decreased from 3.01 ± 0.10% to 1.01 ± 0.01% with 10-mL and 250-mL algal media, and that of Hg(II)-Algae decreased from 0.83 ± 0.13% to 0.22 ± 0.01% with 10-mL and 250-mL Hg(II)-Algae media. Fourier transform infrared spectrometry, surface charge properties and elemental compositions of S. costatum were used to infer that amine, carboxyl and sulfonate functional groups were most likely to interact with Hg(II) through complexation and/or electrostatic attraction. These results suggest that red-tide algae may be an influencing factor on bacterial Hg methylation in eutrophic water bodies., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Using sodium alginate hydrogel as skeleton, in combination with chitosan and magnetic Fe 3 O 4 , a new type of magnetic chitosan/sodium alginate gel bead (MCSB) was prepared. Adsorptive removal of Cu(II) from aqueous solutions was studied by using the MCSB as a promising candidate in environmental application. Different kinetics and isotherm models were employed to investigate the adsorption process. Based on Fourier transform infrared spectroscopy, field-emission scanning electron microscope, CHNS/O elements analysis, vibration magnetometer, and various means of characterization, a comprehensive analysis of the adsorption mechanism was conducted. The MCSB had a good magnetic performance with a saturation magnetization of 12.5 emu/g. Elemental analysis proved that the addition of chitosan introduced a considerable amount of nitrogen-rich groups, contributing significantly to copper adsorption onto gel beads. The contact time necessary for adsorption was optimized at 120 min to achieve equilibrium. Experimental data showed that the adsorption process agreed well with the Langmuir isotherm model and the pseudo-second-order kinetics model. The theoretical maximum adsorption capacity of MCSB for Cu(II) could reach as high as 124.53 mg/g. In conclusion, the MCSB in this study is a novel and promising composite adsorbent, which can be applied for practical applications in due course.

Bacterial community structure and iron corrosion were investigated for simulated drinking water distribution systems (DWDSs) composed of annular reactors incorporating three different treatments: ozone, biologically activated carbon and chlorination (O 3 -BAC-Cl 2 ); ozone and chlorination (O 3 -Cl 2 ); or chlorination alone (Cl 2 ). The lowest corrosion rate and iron release, along with more Fe 3 O 4 formation, occurred in DWDSs with O 3 -BAC-Cl 2 compared to those without a BAC filter. It was verified that O 3 -BAC influenced the bacterial community greatly to promote the relative advantage of nitrate-reducing bacteria (NRB) in DWDSs. Moreover, the advantaged NRB induced active Fe(III) reduction coupled to Fe(II) oxidation, enhancing Fe 3 O 4 formation and inhibiting corrosion. In addition, O 3 -BAC pretreatment could reduce high-molecular-weight fractions of dissolved organic carbon effectively to promote iron particle aggregation and inhibit further iron release. Our findings indicated that the O 3 -BAC treatment, besides removing organic pollutants in water, was also a good approach for controlling cast iron corrosion and iron release in DWDSs., (Copyright © 2017. Published by Elsevier B.V.)

Aphantoxins from Aphanizomenon flos-aquae are frequently identified in eutrophic waterbodies worldwide. These toxins severely endanger environmental safety and human health due to the production of paralytic shellfish poisons (PSPs). Although the molecular mechanisms of aphantoxin neurotoxicity have been studied, many questions remain to be resolved such as in vivo alterations in branchial histology and neurotransmitter inactivation induced by these neurotoxins. Aphantoxins extracted from a naturally isolated strain of A. flos-aquae DC-1 were determined by high performance liquid chromatography. The basic components of the isolated aphantoxins identified were gonyautoxin 1 (GTX1), gonyautoxin 5 (GTX5), and neosaxitoxin (neoSTX), which comprised 34.04, 21.28, and 12.77% of the total, respectively. Zebrafish (Danio rerio) was administrated 5.3 or 7.61mg STX equivalents (eq)/kg (low and high doses, respectively) of the A. flos-aquae DC-1 aphantoxins by intraperitoneal injection. Histological alterations and changes in neurotransmitter inactivation in the gills of zebrafish were investigated for 24h following exposure. Aphantoxin exposure significantly increased the activities of gill alanine aminotransferase (ALT) and aspartate aminotransferase (AST) and resulted in histological alterations in the gills during the first 12h of exposure, indicating the induction of functional and structural damage. Gill acetylcholinesterase (AChE) and monoamine oxidase (MAO) activities were inhibited significantly, suggesting an alteration of neurotransmitter inactivation in zebrafish gills. The observed alterations in gill structure and function followed a time- and dose-dependent pattern. The results demonstrate that aphantoxins or PSPs lead to structural damage and altered function in the gills of zebrafish, including changes in histological structure and increases in the activities of AST and ALT. The inhibition of the activities of AChE and MAO suggest that aphantoxins or PSPs could induce respiratory toxicity in the zebrafish gill. Furthermore, these parameters may be used as bioindicators for investigating aphantoxin exposure and cyanobacterial blooms in nature., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Sewage sludge and bagasse were used as raw materials to produce cheap and efficient adsorbent with great adsorption capacity of Pb(2+). By pyrolysis at 800 °C for 0.5 h, the largest surface area (806.57 m(2)/g) of the adsorbent was obtained, enriched with organic functional groups. The optimal conditions for production of the adsorbent and adsorption of Pb(2+) were investigated. The results of adsorb-ability fitted the Langmuir isotherm and pseudo-second-order model well. The highest Pb(2+) (at pH = 4.0) adsorption capacity was achieved by treating with 60% (v/v) HNO3. This is a promising approach for metal removal from wastewater, as well as recycling sewage sludge and bagasse to ease their disposal pressure., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Nanoscale LaFeO(3) was prepared via sol-gel method and characterized by XRD, FTIR and N2 adsorption/desorption experiment. The results indicated that, LaFeO(3) had a typical perovskite structure with a BET area of 8.5m(2)/g. LaFeO(3) exhibited excellent Fenton activity and stability for the degradation of pharmaceuticals and herbicides in water, as demonstrated with sulfamethoxazole, phenazone, phenytoin, acyclovir and 2,4-dichlorophenoxyacetic acid, 2-chlorophenol. Among them, sulfamethoxazole (SMX) could be completely removed in LaFeO(3)-H(2)O(2) system after reaction for 120 min at neutral pH. Based on the ATR-FTIR analysis, the surface complex of LaFeO(3) and H(2)O(2). was formed, which was important and essential for the enhanced Fenton reaction by accelerating the cycle of Fe(3+)/Fe(2+). Hence, more OH and O(2)(-)/HO(2)(-) were then produced in LaFeO(3)-H(2)O(2) system, resulting in more efficient removal of refractory organic compounds. Based on the surface interaction of LaFeO(3) and H(2)O(2), a heterogeneous Fenton reaction mechanism was proposed., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Aphanizomenon flos-aquae secretes paralytic shellfish poisons (PSPs), termed aphantoxins, and endangers environmental and human health via eutrophication of water worldwide. Although the molecular mechanism of neuronal PSP toxicity has been well studied, several issues remain unresolved, notably the in vivo hepatic antioxidative responses to this neurotoxin. Aphantoxins extracted from a natural isolate of A. flos-aquae DC-1 were resolved by high performance liquid chromatography. The primary components were gonyautoxins 1 and 5 and neosaxitoxin. Zebrafish (Danio rerio) were treated intraperitoneally with either 5.3 or 7.61 (low and high doses, respectively) μg saxitoxin (STX) equivalents (eq)/kg of A. flos-aquae DC-1 aphantoxins. Antioxidative responses in zebrafish liver were examined at different timepoints 1-24h post-exposure. Aphantoxin administration significantly enhanced hepatic malondialdehyde (MDA) content 1-12h post-exposure, indicative of oxidative stress and lipid peroxidation. By contrast, levels of reduced glutathione (GSH) in zebrafish liver declined significantly after 3-24h exposure, suggesting that GSH participates in MDA metabolism. A significant upregulation of the activities of superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPx) was observed, suggesting that aphantoxins induce lipid peroxidation in zebrafish liver and are likely to be hepatotoxic. Hepatic levels of MDA and GSH, and of the three enzymes (SOD, CAT, and GPx), therefore provide potential biomarkers for studying environmental exposure to aphantoxins/PSPs from cyanobacterial blooms., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Aphanizomenon flos-aquae is a cyanobacterium that produces neurotoxins or paralytic shellfish poisons (PSPs) called aphantoxins, which present threats to environmental safety and human health via eutrophication of water bodies worldwide. Although the molecular mechanisms of this neurotoxin have been studied, many questions remain unsolved, including those relating to in vivo hepatic neurotransmitter inactivation, physiological detoxification and histological and ultrastructural alterations. Aphantoxins extracted from the natural strain of A. flos-aquae DC-1 were analyzed by high-performance liquid chromatography. The main components were gonyautoxins 1 and 5 (GTX1, GTX5) and neosaxitoxin (neoSTX), which comprised 34.04%, 21.28%, and 12.77% respectively. Zebrafish (Danio rerio) were exposed intraperitoneally to 5.3 or 7.61 μg STX equivalents (eq)/kg (low and high doses, respectively) of A. flos-aquae DC-1 aphantoxins. Morphological alterations and changes in neurotransmitter conduction functions of acetylcholinesterase (AChE) and monoamine oxidase (MAO) in zebrafish liver were detected at different time points 1-24h post-exposure. Aphantoxin significantly enhanced hepatic alanine aminotransferase (ALT) and aspartate aminotransferase (AST) activities and histological and ultrastructural damage in zebrafish liver at 3-12 h post-exposure. Toxin exposure increased the reactive oxygen species content and reduced total antioxidative capacity in zebrafish liver, suggesting oxidative stress. AChE and MAO activities were significantly inhibited, suggesting neurotransmitter inactivation/conduction function abnormalities in zebrafish liver. All alterations were dose- and time-dependent. Overall, the results indicate that aphantoxins/PSPs induce oxidative stress through inhibition of AChE and MAO activities, leading to neurotoxicity in zebrafish liver. The above parameters may be useful as bioindicators for investigating aphantoxins/PSPs and cyanobacterial blooms in nature., (Copyright © 2014. Published by Elsevier B.V.)

Biogenic manganese oxides (BioMnOx) were synthesized by the oxidation of Mn(II) with Mn-oxidizing bacteria Pseudomonas sp. G7 under different initial pH values and Mn(II) dosages, and were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and UV-Vis absorption spectroscopy. The crystal structure and Mn oxidation states of BioMnOx depended on the initial pH and Mn(II) dosages of the medium. The superoxide radical (O(·-)2) was observed in Mn-containing (III/IV) BioMnOx suspensions by electron spin resonance measurements. BioMnOx(0.4)-7, with mixed valence of Mn(II/III/IV) and the strongest O(·-)2 signals, was prepared in the initial pH 7 and Mn(II) dosage of 0.4 mmol/L condition, and exhibited the highest activity for ciprofloxacin degradation and no Mn(II) release. During the degradation of ciprofloxacin, the oxidation of the Mn(II) formed came from biotic and abiotic reactions in BioMnOx suspensions on the basis of the Mn(II) release and O(·-)2 formation from different BioMnOx. The degradation process of ciprofloxacin was shown to involve the cleavage of the hexatomic ring having a secondary amine and carbon-carbon double bond connected to a carboxyl group, producing several compounds containing amine groups as well as small organic acids., (Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.)

Aphanizomenon flos-aquae is a cyanobacterium that is frequently encountered in eutrophic waters worldwide. It is source of neurotoxins known as aphantoxins or paralytic shellfish poisons (PSPs), which present a major threat to the environment and human health. The molecular mechanism of PSP action is known, however the in vivo effects of this neurotoxin on oxidative stress, lipid peroxidation and the antioxidant defense responses in zebrafish brain remain to be understood. Aphantoxins purified from a natural isolate of A. flos-aquae DC-1 were analyzed using high performance liquid chromatography. The major components of the toxins were gonyautoxins 1 and 5 (GTX1 and GTX5, 34.04% and 21.28%, respectively) and neosaxitoxin (neoSTX, 12.77%). Zebrafish (Danio rerio) were injected intraperitoneally with 7.73 μg/kg (low dose) and 11.13 μg/kg (high dose) of A. flos-aquae DC-1 aphantoxins. Oxidative stress, lipid peroxidation and antioxidant defense responses in the zebrafish brain were investigated at various timepoints at 1-24h post-exposure. Aphantoxin exposure was associated with significantly increased (>1-2 times) reactive oxygen species (ROS) and malondialdehyde (MDA) in zebrafish brain compared with the controls at 1-12h postexposure, suggestive of oxidative stress and lipid peroxidation. In contrast, reduced glutathione (GSH) levels in the zebrafish brain exposed to high or low doses of aphantoxins decreased by 44.88% and 41.33%, respectively, after 1-12h compared with the controls, suggesting that GSH participated in detoxification to ROS and MDA. Further analysis showed a significant increase in the activities of superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPx) compared with the controls, suggesting elimination of oxidative stress by the antioxidant response in zebrafish brain. All these changes were dose and time dependent. These results suggested that aphantoxins or PSPs increased ROS and MDA and decreased GSH in zebrafish brain, and these changes induced oxidative stress. The increased activity of SOD, CAT and GPx demonstrated that these antioxidant enzymes could play important roles in eliminating excess ROS and MDA. These results also suggest that MDA, ROS, GSH and these three antioxidant enzymes in the brain of zebrafish may act as bioindicators for investigating A. flos-aquae DC-1 aphantoxins or PSPs and algal blooms in nature., (Copyright © 2013 Elsevier B.V. All rights reserved.)

This study confirmed the feasibility of natural limonite working as the iron catalyst for the PNP wastewater treatment in the BES-Fenton system. After the start-up period of the BES-Fenton systems, air and limonite powder were injected into the cathode chamber as the original materials for manufacturing Fenton reagents of H₂O₂ and Fe(II) respectively. The experiment parameters like pH, external resistance, limonite dosage and initial PNP concentration were investigated in this research. The removal efficiency of PNP (0.25 mM) could achieve 96% in 6h under the optimal experimental conditions. A limonite dosage of 112 mg per 50 ml of PNP solution at 0.25 mM concentration each time could sustain 7 cycles of the BES-Fenton system operation with PNP removal efficiency >94%. This study suggests an efficiency and cost-effective approach for the PNP removal by using the natural limonite as the iron catalyst of the BES-Fenton system., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The cathodic reduction of complex-state copper(II) was investigated in a dual chamber microbial fuel cell (MFC). The inner resistance of MFC system could be reduced in the presence of ionizing NH(4)(+), however, mass transfer was hindered at higher ammonia concentration. Thermodynamic and electrochemical analyses indicated that the processes of complex dissociation and copper reduction were governed by the ratio of T[Cu]:T[NH(3)] and the pH of solution. The reduction of Cu(NH(3))(4)(2+) could be achieved via two possible pathways: (1) releasing Cu(2+) from Cu(NH(3))(4)(2+), then reducing Cu(2+) to Cu or Cu(2)O and (2) Cu(NH(3))(4)(2+) accepting an electron and forming Cu(NH(3))(2)(+), and depositing as Cu or Cu(2)O consequently. At initial concentration of 350 mg T[Cu] L(-1), copper removal efficiency of 96% was obtained at pH=9.0 within 12 h (with △Cu/△COD=1.24), 84% was obtained at pH=3.0 within 8 h (with △Cu/△COD=1.72). Cu(NH(3))(4)(2+) was reduced as polyhedral deposits on the cathode., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Aluminum-modified hydroxyapatite (Al-HAP) was prepared and characterized using XRD and BET analyses. Al-HAP possessed higher defluoridation capacity (DC) of 32.57 mgF(-)/g than unmodified hydroxyapatite (HAP) which showed a DC of 16.38 mgF(-)/g. The effect of Al/Ca atomic ratio in Al-HAP, solution pH and co-existing anions was further studied. The results indicated that the adsorption data could be well described by the Langmuir isotherm model and the adsorption kinetic followed the pseudo-second-order model. The pH changes during the adsorption process suggested that the OH on the surface of Al-HAP was the adsorption sites. The more adsorption sites were formed on Al modified HAP, which possessed abundant surface hydroxyl groups, resulting in higher efficiency of F(-) removal. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated in order to understand the nature of adsorption process. The results revealed that the adsorption reaction was a spontaneous and endothermic process., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Great efforts have been made in China to retrofit and upgrade the existing municipal wastewater treatment plants (WWTPs) for enhanced removal of organic substrates and in particular nutrients. However, the removal of trace recalcitrant or hazardous organic chemicals, e.g. steroid estrogens, one group of typical endocrine disrupting chemicals, has long been overlooked. The extensive investigations on estrogen removal rates in global and Chinese WWTPs and the estrogen biodegradation kinetics results in batch laboratory experiments are reviewed in this study. The effects of estrogen initial concentration and nitrifying activated sludge are highlighted. Challenges existing in current estrogen studies are pointed out, which are relevant for researches on fate and behavior of similar down-the-drain chemicals in both Chinese and global WWTPs., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The aqueous photodegradation of the widely used antibiotic chlortetracycline (CTC) was investigated under simulated sunlight. The quantum yield of photodegradation increased from 3.3 x 10(-4) to 8.5 x 10(-3) within the pH range of 6.0 to 9.0. The presence of Ca2+, Fe3+, and NO(-3) enhanced the photodegradation of CTC, whereas Mg2+, Mn2+, and Zn2+ inhibited the degradation with the order Mn2+ > Zn2+ > Mg2+ at pH 7.3. The monovalent cations (Na+ and K+) had negligible effect on the photolysis of CTC. Fulvic acid (FA) decreased the photodegradation of CTC due to light screening effect. Hydrogen peroxide (H2O2) was formed concurrently with direct photodegradation of CTC. The generation rate of H2O2 increased from 0.027 to 0.086 micromol/(L x min) when the pH ranged from 6.0 to 9.0. The CTC solution was about three-fold more toxic to the Photobacterium phosphoreum bacteria after irradiation, suggesting that the photoproducts and H2O2 formed in the CTC solution exhibited high risk on the bacteria. By LC-ESI(+)-MS, the photoproducts of CTC were identified. The direct photodegradation of CTC was involved in hydroxylation and N-demethyl/dedismethyl processes. The main photoproducts included the iso-CTC analog containing hydroxyl groups (m/z 511.4 and 495.4), and the N-demethyl/dedismethyl products of the photoproduct m/z 495.4 (m/z 481.3 and 467.4). In addition, the photochemical dechlorination of CTC led to tetracycline (m/z 445.5).

Based on energetic analysis, a novel approach for copper electrodeposition via cathodic reduction in microbial fuel cells (MFCs) was proposed for the removal of copper and recovery of copper solids as metal copper and/or Cu(2)O in a cathode with simultaneous electricity generation with organic matter. This was examined by using dual-chamber MFCs (chamber volume, 1L) with different concentrations of CuSO(4) solution (50.3 ± 5.8, 183.3 ± 0.4, 482.4 ± 9.6, 1007.9 ± 52.0 and 6412.5 ± 26.7 mg Cu(2+)/L) as catholyte at pH 4.7, and different resistors (0, 15, 390 and 1000 Ω) as external load. With glucose as a substrate and anaerobic sludge as an inoculum, the maximum power density generated was 339 mW/m(3) at an initial 6412.5 ± 26.7 mg Cu(2+)/L concentration. High Cu(2+) removal efficiency (>99%) and final Cu(2+) concentration below the USA EPA maximum contaminant level (MCL) for drinking water (1.3mg/L) was observed at an initial 196.2 ± 0.4 mg Cu(2+)/L concentration with an external resistor of 15 Ω, or without an external resistor. X-ray diffraction analysis confirmed that Cu(2+) was reduced to cuprous oxide (Cu(2)O) and metal copper (Cu) on the cathodes. Non-reduced brochantite precipitates were observed as major copper precipitates in the MFC with a high initial Cu(2+) concentration (0.1M) but not in the others. The sustainability of high Cu(2+) removal (>96%) by MFC was further examined by fed-batch mode for eight cycles., (Copyright © 2011 Elsevier B.V. All rights reserved.)

A membrane-free baffled microbial fuel cell (MFC) was developed to treat synthetic Cu(II) sulfate containing wastewater in cathode chamber and synthetic glucose-containing wastewater fed to anode chamber. Maximum power density of 314 mW/m(3) with columbic efficiency of 5.3% was obtained using initial Cu(2+) concentration of 6400 mg/L. Higher current density favored the cathodic reduction of Cu(2+), and removal of Cu(2+) by 70% was observed within 144 h using initial concentration of 500 mg/L. Powder X-ray diffraction (XRD) analysis indicated that the Cu(2+) was reduced to Cu(2)O or Cu(2)O plus Cu which deposited on the cathode, and the deficient cathodic reducibility resulted in the formation of Cu(4)(OH)(6)SO(4) at high initial Cu(2+) concentration (500-6400 mg/L). This study suggested a novel low-cost approach to remove and recover Cu(II) from Cu(2+)-containing wastewater using MFC-type reactor., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

Tetracyclines constitute one of the most important antibiotic families and represent a classic example of phototoxicity. The photoproducts of tetracyclines and their parent compounds have potentially adverse effects on natural ecosystem. In this study, the self-sensitized oxidation products of tetracycline (TC) and oxytetracycline (OTC) were determined and the effects of Ca2+ and Mg2+ on self-sensitized degradation were investigated. The Ca2+ and Mg2+ in the natural water sample accounted for enhancement (pH 7.3) and inhibition (pH 9.0) of photodegradation of TC and OTC due to the formation of metal-ions complexes. The formation of Mg2+ complexes was unfavorable for the photodegradation of the tetracyclines at both pH values. In contrast, the Ca2+ complexes facilitated the attack of singlet oxygen (1O2) arising from self-sensitization at pH 7.3 and enhanced TC photodegradation. For the first time, self-sensitized oxidation products of TC and OTC were verified by quenching experiments and detected by LC/ESI-DAD-MS. The products had a nominal mass 14 Da higher than the parent drugs (designated M+14), which resulted from the 1O2 attack of the dimethylamino group on the C-4 atom of the tetracyclines. The presence of Ca2+ and Mg2+ also affected the generation of M+14 due to the formation of metal-ions complexes with TC and OTC. The findings suggest that the metal-ion complexation has significant impact on the self-sensitized oxidation processes and the photoproducts of tetracyclines.

A new biomimetic absorbent, cellulose acetate (CA) embedded with triolein (CA-triolein), was prepared and applied for the removal of persistent organic pollutants (POPs) from micro-polluted aqueous solution. The comparison of CA-triolein, CA and granular activated carbon (GAC) for dieldrin removal was investigated. Results showed that CA-triolein absorbent gave a lowest residual concentration after 24 h although GAC had high removal rate in the first 4 h adsorption. Then the removal efficiency of mixed POPs (e.g. aldrin, dieldrin, endrin and heptachlor epoxide), absorption isotherm, absorbent regeneration and initial column experiments of CA-triolein were studied in detail. The linear absorption isotherm and the independent absorption in binary isotherm indicated that the selected POPs are mainly absorbed onto CA-triolein absorbent by a partition mechanism. The absorption constant, K, was closely related to the hydrophobic property of the compound. Thermodynamic calculations showed that the absorption was spontaneous, with a high affinity and the absorption was an endothermic reaction. Rinsing with hexane the CA-triolein absorbent can be regenerated after absorption of POPs. No significant decrease in the dieldrin removal efficiency was observed even when the absorption-regeneration process was repeated for five times. The results of initial column experiments showed that the CA-triolein absorbent did not reach the breakthrough point at a breakthrough empty-bed volume (BV) of 3200 when the influent concentration was 1-1.5 microg/L and the empty-bed contact time (EBCT) was 20 min.

SiO2-C2H4-ferrocene (SiCFe) was synthesized by covalent grafting of ferrocene on functionalized silica gel with a -C2H4- linkage. On the basis of characterization by diffuse reflectance UV-vis spectra (DRS) and Fourier transform infrared spectra (FT-IR), ferrocene has been successfully anchored on the silica gel. Under UVA (lambdamax=365 nm) irradiation, the catalyst exhibited high photocatalytic activity in the degradation of Acid Red B (ARB), especially in the presence of H2O2. Meanwhile, the catalytic activity of SiCFe was maintained effectively even after reused for 4 times without any significant destruction of ferrocene. The influence of initial solution pH and wavelength of UV light on the catalyst's activity was also investigated. Electron spin resonance (ESR) studies revealed that both OH and HO2/O2- radicals were involved as the active species in the ARB degradation process. Furthermore, results of total organic carbon (TOC) and FT-IR analysis indicated that ARB degradation proceeded by the cleavage of NN, followed by hydroxylation and opening of phenyl rings to form aliphatic acids and further oxidization of the aliphatic acids to produce carbon dioxide and water. A possible reaction mechanism was proposed on the basis of all the information obtained under various experimental conditions.

Nitrobenzene (NB) pollution of the Songhua River caused by an explosion at a petrochemical plant in Jilin City, Jilin Province, China, attracted public concern over the fate of NB in the river. As one of the efforts to predict the fate of residual NB in the river, the kinetics and mechanism of phototransformation of NB in natural water from four sections of the Songhua River were investigated. It was found that photodegradation of NB in water proceeded via pseudo-first-order reaction kinetics under simulated solar irradiation conditions, and the rate constant (k) in the ultrapure water system was 0.0168 h(-1), which was approximately half of those in the natural river water systems (0.323-0.402 h(-1)). The relatively short half-life of NB in natural river water systems (17.2-21.5 h) indicates that photodegradation might have played an important role in the loss of NB flux in the river. Nitrate concentration and alkalinity were the two main factors affecting the photochemical fate of NB, suggesting that decomposition of NB mediated by .OH was predominant in water solution with high nitrate concentrations. Three isomeric nitrophenols, o-, m-, and p-nitrophenols, as well as phenol were detected as the main organic products in natural water under natural and simulated solar irradiations.