Efficient Proton-exchange Membrane Fuel Cell Performance of Atomic Fe Sites via p-d Hybridization with Al Dopants.

Orbital hybridization to regulate the electronic structures and surface chemisorption properties of transition metals is of great importance for boosting the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). Herein, we developed a core-shell rambutan-like nanocarbon catalyst (FeAl-RNC) with atomically dispersed Fe-Al atom pairs from metal-organic framework (MOF) material. Experimental and theoretical results demonstrate that the strong p-d orbital hybridization between Al and Fe results in an asymmetric electron distribution with moderate adsorption strength of oxygen intermediates, rendering enhanced intrinsic ORR activity. Additionally, the core-shell rambutan-like structure of FeAl-RNC with abundant micropores and macropores can enhance the density of active sites, stability, and transport pathways in PEMFC. The FeAl-RNC-based PEMFC achieves excellent activity (68.4 mA cm-2 at 0.9 V), high peak power (1.05 W cm-2), and good stability with only 7% current loss after 100 h at 0.7 V under H2-O2 condition.

Hydroxyl Defects-Mediated Hydrolytic Activation of Peroxydisulfate Under Nanoconfinement: Role of Lewis Basic Sites for Altering the Photosensitized Species and Pathways.

Herein, the pivotal mechanism of defect engineering-mediated triazine-based conjugated polymers (TCPs) is comprehensively elucidated for photosensitized activation of peroxydisulfate (PDS) under nanoconfinement by encapsulating the defective polymer framework into the nanochannel of SBA-15 (d-TCPs@SBA-15). The incorporated hydroxyl defects (-OH defects) substantially accelerate the accumulation of electrons at -OH defects, forming the Lewis basic sites. Due to the facilitated elongation of the S─O bond and reduced energy barrier of SO5* generation, the captured PDS undergo prehydrolysis process, oxidized into O2 - and 1O2 by surrounding h+, thereby setting apart from the conventional reductive activation of SO4 -/•OH generation occurred in pristine TCPs (p-TCPs). Crucially, this work represents a pioneering effort in exploring the PDS activation pathway upon the defective polymer under the nanoconfinement to leverage kinetic merits of slow photon effect and reactive oxygen species (ROSs) enrichment, and the novel prehydrolysis activation mechanism involved may catalyze the rational design of photocatalysts featuring Lewis-acid/base centers.

Surface Coordination of Garnet Fillers Improves the Organic-Inorganic Interfacial Compatibility of Composite Solid Electrolyte.

Composite solid electrolytes (CSEs) have become one of the most promising solid-state electrolytes due to their favorable safety and flexibility. However, the weak interaction between inorganic fillers and polymer matrix leads to poor organic-inorganic interfacial compatibility, which degrades the electrochemical performance of CSEs. Herein, it is demonstrated that Li6.4La3Zr1.4Ta0.6O12 (LLZTO) can be chemically bonded to the polymer matrix by surface coordination of the 1,2-dithiolane group of lipoic acid (LA) with metal atoms on the surface of LLZTO through a combination of experimental investigations and theoretical calculations. The surface coordination not only enhances the interfacial compatibility between LLZTO and the polymer matrix, but also facilitates rapid Li+ transport, which leads to the ionic conductivity of the prepared CSE (P-V-M@LLZTO) as high as 6.1 × 10-4 S cm-1 at 30 °C. The excellent interface compatibility ensures a stable cycle of Li/P-V-M@LLZTO/Li symmetrical cell for more than 3500 h. As a result, LiFePO4/P-V-M@LLZTO/Li cell delivers the discharge capacity of 161 mAh g-1 after 5 cycles with a capacity retention of 81% after 500 cycles at 0.5C under 30 °C. This work demonstrates that surface coordination is an effective strategy to solve the inherent interfacial incompatibility problem in CSEs.

Unveiling the Mechanism and Kinetics of Pollutant Attenuation by Free Radicals Triggered from Goethite in Water Distribution Systems.

Investigating the fate of persistent organic pollutants in water distribution systems (WDSs) is of great significance for preventing human health risks. The role of iron corrosion scales in the migration and transformation of organics in such systems remains unclear. Herein, we determined that hydroxyl (•OH), chlorine, and chlorine oxide radicals are generated by Fenton-like reactions due to the coexistence of oxygen vacancy-related Fe(II) on goethite (a major constituent of iron corrosion scales) and hypochlorous acid (HClO, the main reactive chlorine species of residual chlorine at pH ∼ 7.0). •OH contributed mostly to the decomposition of atrazine (ATZ, model compound) more than other radicals, producing a series of relatively low-toxicity small molecular intermediates. A simplified kinetic model consisting of mass transfer of ATZ and HClO, •OH generation, and ATZ oxidation by •OH on the goethite surface was developed to simulate iron corrosion scale-triggered residual chlorine oxidation of organic compounds in a WDS. The model was validated by comparing the fitting results to the experimental data. Moreover, the model was comprehensively applicable to cases in which various inorganic ions (Ca2+, Na+, HCO3-, and SO42-) and natural organic matter were present. With further optimization, the model may be employed to predict the migration and accumulation of persistent organic pollutants under real environmental conditions in the WDSs.

Atomically Dispersed Fe-N4 Site as a Conductive Bridge Enables Efficient and Stable Activation of Peroxymonosulfate: Active Site Renewal, Anti-Oxidative Capacity, and Pathway Alternation Mechanism.

Atomically dispersed metal sites anchored on nitrogen-doped carbonaceous substrates (M-NCs) have emerged as promising alternatives to conventional peroxymonosulfate (PMS) activators; however, the exact contribution of each site still remains elusive. Herein, isolated Fe-N4 active site-decorated three-dimensional NC substrates (FeSA-NC) via a micropore confinement strategy are fabricated to initiate PMS oxidation reaction, achieving a specific activity of 5.16 × 103 L·min-1·g-1 for the degradation of bisphenol A (BPA), which outperforms most of the state-of-the-art single-atom (SA) catalysts. Mechanism inquiry reveals enhanced chemisorption and electron transfer between PMS and FeSA-NC, enabling an inner electron shuttle mechanism in which Fe-N4 serves as a conductive bridge. The Fe-N4 sites reduce the energy barrier for the formation of SO5* and H*, thereby transforming the reaction pathway from directly adjacent electron transfer into reactive oxygen species (ROS)-dominated oxidation. Theoretical calculations and dynamic simulations reveal that the Fe-N4 sites induce facilitated desorption of reaction intermediates (PMS*/BPA*), which collectively contribute to the renewal of active sites and eventually enhance the catalytic durability. This work offers a reasonable interpretation for the important role of the Fe-N4 moiety in altering the activation mechanism and enhancing the antioxidative capacity of NC materials, which fundamentally furnishes theoretical support for SA material design.

Covalent Triazine Frameworks with Defective Accumulation Sites: Exceptionally Modulated Electronic Structure for Solar-Driven Oxidative Activation of Peroxymonosulfate.

Precisely tailoring the electronic structure and surface chemistry of metal-free covalent triazine frameworks (CTFs) for efficient photoactivation of oxyanions is environmentally desirable but still challenging. Of interest to us in this work was to construct artificial defective accumulation sites into a CTF network (CTF-SDx) to synchronously modulate both thermodynamic (e.g., band structure) and kinetic (e.g., charge separation/transfer/utilization and surface adsorption) behaviors and probe how the transformation affected the subsequent activation mechanism of peroxymonosulfate (PMS). With the incorporation of terminal cyano (-CN) groups and boron (B) dopants, the delocalized CTF-SD underwent a narrowed electronic energy gap for increased optical absorption as well as a downshifted valence band position for enhanced oxidation capacity. Moreover, the localized charge accumulation regions induced by the electron-withdrawing -CN groups facilitated the exciton dissociation process, while the adjacent electron-deficient areas enabled strong affinity toward PMS molecules. All of these merits impelled the photoactivation reaction with PMS, and a 15-fold enhancement of bisphenol-A (BPA) removal was found in the CTF-SD2/PMS/vis system compared with the corresponding pristine CTF system. Mechanistic investigations demonstrated that this system decomposed organics primarily through a singlet oxygen-mediated nonradical process, which originated from PMS oxidative activation over photoinduced holes initiated by an electron transfer process, thereby opening a new avenue for designing an efficient PMS activation strategy for the selective oxidation of organic pollutants.

Oxidation of chloroquine drug by ferrate: Kinetics, reaction mechanism and antibacterial activity.

Chloroquine (CLQ) is required to manufacture on a larger scale to combat COVID-19. The wastewater containing CLQ will be discharged into the natural water, which was resistant to environmental degradation. Herein, the degradation of CLQ by ferrate (Fe(VI)) was investigated, and the biodegradability of the oxidation products was examined to evaluate the potential application in natural water treatment. The reaction between CLQ and Fe(VI) was pH-dependent and followed second-order kinetics. The species-specific rate constant of protonated Fe(VI) species (HFeO4 -) was higher than that of the FeO4 2- species. Moreover, increasing the reaction temperature could increase the degradation rate of CLQ. Besides, HCO3 - had positive effect on CLQ removal, while HA had negative effect on CLQ removal. But the experiments shows Fe(VI) could be used as an efficient technique to degrade co-existing CLQ in natural waters. During the oxidation, Fe(VI) attack could lead to aromatic ring dealkylation and chloride ion substitution to form seven intermediate products by liquid chromatography-time-of-flight-mass spectrometry (LC-TOF-MS) determination. Finally, a pure culture test showed that the oxidation of CLQ by Fe(VI) could slightly increase the antimicrobial effect towards Escherichia coli (E.coli) and reduce the toxicity risk of intermediates. These findings might provide helpful information for the environmental elimination of CLQ.

Disinfection byproduct formation from algal organic matters after ozonation or ozone combined with activated carbon treatment with subsequent chlorination.

Algal organic matter (AOM), including extracellular organic matter (EOM) and intracellular organic matter (IOM) from algal blooms, is widely accepted as essential precursors of disinfection byproducts (DBPs). This study evaluated the effect of ozonation or ozone combined with activated carbon (O3-AC) treatment on characteristic alternation and DBP formation with subsequent chlorination of Chlorella sp.. The effects of pH and bromide concentration on DBP formation by ozonation or O3-AC treatment were also investigated. Results showed that the potential formation of DBPs might be attributed to ozonation, but these DBP precursors could be further removed by activated carbon (AC) treatment. Moreover, the formation of target DBPs was controlled at acidic pH by alleviating the reactions between chlorine and AOM. Besides, the bromide substitution factor (BSF) value of trihalomethanes (THMs) from EOM and IOM remained constant after AC treatment. However, THM precursors could be significantly decreased by AC treatment. The above results indicated that O3-AC was a feasible treatment method for algal-impacted water.

Degradation of sulfonamides and formation of trihalomethanes by chlorination after pre-oxidation with Fe(VI).

Sulfonamides are used in human therapy, animal husbandry and agriculture but are not easily biodegradable, and are often detected in surface water. Sulfamethazine (SMZ) and sulfadiazine (SDZ) are two widely used sulfonamide antibiotics that are used heavily in agriculture. In this study, they were degraded in an aqueous system by chlorination after pre-oxidation with ferrate(VI) (FeVIO42-, Fe(VI)), an environmentally friendly oxidation technique that has been shown to be effective in degrading various organics. The kinetics of the degradation were determined as a function of Fe(VI) (0-1.5mg/L), free chlorine (0-1.8mg/L) and temperature (15-35°C). According to the experimental results, SMZ chlorination followed second-order kinetics with increasing Fe(VI) dosage, and the effect of the initial free chlorine concentration on the reaction kinetics with pre-oxidation by Fe(VI) fitted a pseudo-first order model. The rate constants of SDZ and SMZ chlorination at different temperatures were related to the Arrhenius equation. Fe(VI) could reduce the levels of THMs formed and the toxicity of the sulfonamide degradation systems with Fe(VI) doses of 0.5-1.5mg/L, which provides a reference for ensuring water quality in drinking water systems.

Mechanical energy triggered piezo-catalyzation of Bi2WO6 nanoplates on ferrate (Fe(VI)) oxidation in alkaline media: Performance and mechanism.

Piezo-electricity, as a unique physical phenomenon, demonstrates high effectiveness in capturing the environmental mechanical energy into polarization charges, offering the possibility to activate the advanced oxidation processes via the electron pathway. However, information regarding the intensification of Fe(VI) through piezo-catalysis is limited. Therefore, our study is the first to apply Bi2WO6 nanoplates for piezo-catalyzation of Fe(VI) to enhance bisphenol A (BPA) degradation. Compared to Fe(VI) alone, the Fe(VI)/piezo/Bi2WO6 system exhibited excellent BPA removal ability, with the degradation rate increased by 32.6% at pH 9.0. Based on the experimental and theoretical results, Fe(VI), Fe(V), Fe(IV) and •OH were confirmed as reaction active species in the reaction, and the increased BPA removal mainly resulted from the enhanced formation of Fe(IV)/Fe(V) species. Additionally, effects of coexisting anions (e.g., Cl-, NO3-, SO42- and HCO3-), humic acid and different water matrixes (e.g., deionized water, tap water and lake water) on BPA degradation were studied. Results showed the Fe(VI)/piezo/Bi2WO6 system still maintained satisfactory BPA degradation efficiencies under these conditions, guaranteeing future practical applications in surface water treatment. Furthermore, the results of intermediates identification, ECOSAR calculation and cytotoxicity demonstrated that BPA degradation by Fe(VI)/piezo/Bi2WO6 posed a diminishing ecological risk. Overall, these findings provide a novel mechanical energy-driven piezo-catalytic approach for Fe(VI) activation, enabling highly efficient pollutant removal under alkaline condition.

Remodeling Highly Fluorinated Electrolyte via Shielding Agent Regulation toward Practical Lithium Metal Batteries.

Highly fluorinated electrolytes have proved effective in improving electrochemical stability of lithium metal batteries. However, excessive fluorination not only detrimentally impacts the electrolyte ionic conductivity, but also inevitably forms the over-fluorinated interphases with sluggish ion diffusivity. Herein, a strategy on remodeling Li+ solvation structure in highly fluorinated electrolyte aided is proposed by fluorinated amide (FDMA), which denoted as "shielding agent". Benefitting from FDMA's high donor number (DN) value (22.1), the Li+-dipole (fluoroethylene carbonate (FEC) or trans-4,5-Difluoroethylenecarbonate (DFEC)) interaction is interrupted and the participation of FDMA in primary solvation sheath fructify the solid-electrolyte interphase without scarifying the privilege of fluorinated electrolyte on interphase chemistry. Eventually, the optimal high-fluorinated electrolyte (FDMA/DFEC + 1.0 mol L-1 LiTFSI) with this unique shielding effect displays high ionic conductivity and rapid Li+ desolvation behavior, enabling Li||LiNi0.6Co0.2Mn0.2O2 (Li||NCM622) to achieve an ultralong cycle-life of 2000 cycles at 1C with 84.7% capacity retention. Even under extreme conditions (NCM622: 10 mg cm-2; electrolyte: 20 µL; Li: 50 µm), the Li||NCM622 displays excellent electrochemical performance. Additionally, 447 Wh kg-1 Li||LiNi0.8Co0.1Mn0.1O2 (Li||NCM811) pouch cells have been successfully fabricated and demonstrate an exceptional cycle-life over 150 cycles. The proposed "shielding" strategy to modulate the solvation structure paves the way for developing practical LMBs with fluorinated electrolytes.

The occurrence, formation and transformation of disinfection byproducts in the water distribution system: A review.

Disinfection is an effective process to inactivate pathogens in drinking water treatment. However, disinfection byproducts (DBPs) will inevitably form and may cause severe health concerns. Previous research has mainly focused on DBPs formation during the disinfection in water treatment plants. But few studies paid attention to the formation and transformation of DBPs in the water distribution system (WDS). The complex environment in WDS will affect the reaction between residual chlorine and organic matter to form new DBPs. This paper provides an overall review of DBPs formation and transformation in the WDS. Firstly, the occurrence of DBPs in the WDS around the world was cataloged. Secondly, the primary factors affecting the formation of DBPs in WDS have also been summarized, including secondary chlorination, pipe materials, biofilm, deposits and coexisting anions. Secondary chlorination and biofilm increased the concentration of regular DBPs (e.g., trihalomethanes (THMs) and haloacetic acids (HAAs)) in the WDS, while Br- and I- increased the formation of brominated DBPs (Br-DBPs) and iodinated DBPs (I-DBPs), respectively. The mechanism of DBPs formation and transformation in the WDS was systematically described. Aromatic DBPs could be directly or indirectly converted to aliphatic DBPs, including ring opening, side chain breaking, chlorination, etc. Finally, the toxicity of drinking water in the WDS caused by DBPs transformation was examined. This review is conducive to improving the knowledge gap about DBPs formation and transformation in WDS to better solve water supply security problems in the future.

Enabling high-capacity Li metal battery with PVDF sandwiched type polymer electrolyte.

Polyvinylidene difluoride (PVDF) is one of the most attractive electrolyte materials for solid-state batteries due to its high ionic conductivity, however, the battery performance is limited by the high electrolyte-electrode interfacial resistance. Herein, PVDF polymer mixed with ceramic Li7La3Zr2O12 is coated on cellulose support membrane (PLCSM) through a simple slurry-casting method. The ionic transport of PLCSM is originated from dimethyl formamide (DMF)-Li+ solvation structure, which plays a critical role in conducting lithium ions. ß-PVDF after dehydrofluorination offers a high dielectric constant and enhances the dissociation of lithium salt. As a result, PLCSM with a total thickness of 85 µm presents an oxidation voltage of 4.9 V. Li-Li symmetric cells by employing PLCSM reveal that the critical current density (CCD) is increased to 1 mA cm-2. A full cell of LiFePO4 |PLCSM |Li with high mass loading (1.2 mA h cm-2) shows a first-cycle discharge capacity of 160 mA h g-1. With LiNi0.6Mn0.2Co0.2O2 as the cathode, the initial discharge capacity is 153 mA h g-1, and the capacity retention after 80 cycles is 80 %. The sandwiched PLCSM provides an effective strategy to achieve high-performance dendrite-free Li metal batteries.

Boosting photocatalytic H2 evolution on UIO-66-NH2/covalent triazine-based frameworks composites by constructing a covalent heterojunction.

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have been proved as efficient catalysts for photocatalytic hydrogen (H2) evolution, thanks to their tunable functionalities, permanent porosity, excellent visible light response, and physicochemical stability. Herein, a series of photocatalysts (termed NUBC) was fabricated by loading different amounts of Zr-UiO-66-NH2 (NU) onto a benzoic acid-modified covalent triazine-based framework (BC) based on post-synthetic covalent modification. The resulting NUBC catalysts exhibited a type-II Z-scheme heterojunction structure formed via the amide covalent bonds between the amine groups on NU and carboxyl groups on BC. The optimal loading of NU on BC is 30 wt.% (30NUBC) and the corresponding photocatalytic H2 evolution rate was 378 µmol h-1 g-1, almost 445 and 2 times than that of NU and BC, respectively. The synergistic effect between the type-II Z-scheme heterojunctions and amide bonds was conducive to boosting visible light harvesting and facilitating charge transportation and separation. Furthermore, the prepared NUBC catalysts show great reusability and stability. Overall, this work sheds light on the design of novel MOF/COF hybrid materials and provides a systematic exploration of their photocatalytic H2 evolution properties.

Fe(VI) activation system mediated by a solar-driven TiO2 nanotubes electrode for CLQ degradation: Performances, mechanisms and pathways.

Ferrate (Fe(VI), FeO42-) has been widely used in the degradation of micropollutants with the advantages of high redox potential, no secondary pollution and inhibition of disinfection byproducts. However, the low transformation of Fe(V) and/or Fe(IV) by Fe(VI) and incomplete mineralization of pollutants limit their application. In this work, we designed a photo electric cell with TiO2 nanotubes (TNTs) and Pt serving as the anode and cathode to enhance the utilization of Fe(VI) (Fe(VI)-TNTs system). TNTs accelerated the generation of •OH via hVB+ oxidation of OH- and photogenerated electrons at Pt boosted the transformation of Fe(VI) to Fe(V) and/or Fe(IV), resulting in a 22.2 % enhancement of chloroquine (CLQ) removal compared to Fe(VI) alone. The results from EPR and quenching tests showed that Fe(VI), Fe(V), Fe(IV), •OH, O2•- and hVB+ coexisted in the Fe(VI)-TNTs system, among which Fe(V) and Fe(IV) were testified as the primary reactive substances accounting for 59 % of CLQ removal. The performance tests and recycling tests demonstrated that the Fe(VI)-TNTs system maintained excellent performance in an authentic water environment. The plausible degradation pathway of CLQ oxidized in the Fe(VI)-TNTs system was proposed with nine identified oxidation products via N-C cleavage, electrophilic addition and carboxylation processes. Based on the ECOSAR calculation, the constructed reaction system allowed a decrease in acute and chronic toxicity. Our findings provide a highly efficient and cost-effective strategy to enhance Fe(VI) application for micropollutant degradation in the future.

Improving Wastewater Treatment by Triboelectric-Photo/Electric Coupling Effect.

The ability to meet higher effluent quality requirements and the reduction of energy consumption are the biggest challenges in wastewater treatment worldwide. A large proportion of the energy generated during wastewater treatment processes is neglected and lost in traditional wastewater treatment plants. As a type of energy harvesting system, triboelectric nanogenerators (TENGs) can extensively harvest the microscale energies generated from wastewater treatment procedures and auxiliary devices. This harvested energy can be utilized to improve the removal efficiency of pollutants through photo/electric catalysis, which has considerable potential application value in wastewater treatment plants. This paper gives an overall review of the generated potential energies (e.g., water wave energy, wind energy, and acoustic energy) that can be harvested at various stages of the wastewater treatment process and introduces the application of TENG devices for the collection of these neglected energies during wastewater treatment. Furthermore, the mechanisms and catalytic performances of TENGs coupled with photo/electric catalysis (e.g., electrocatalysis, photoelectric catalysis) are discussed to realize higher pollutant removal efficiencies and lower energy consumption. Then, a thorough, detailed investigation of TENG devices, electrode materials, and their coupled applications is summarized. Finally, the intimate coupling of self-powered photoelectric catalysis and biodegradation is proposed to further improve removal efficiencies in wastewater treatment. This concept is conducive to improving knowledge about the underlying mechanisms and extending applications of TENGs in wastewater treatment to better solve the problems of energy demand in the future.

Insights into the mechanisms of tris(2-chloroethyl) phosphate-induced growth inhibition in juvenile yellow catfish Pelteobagrus fulvidraco.

With the gradual elimination of brominated flame retardants (BFRs), the production and application of tris (2-chloroethyl) phosphate (TCEP), as a substitute of BFRs, has increased greatly. The objective of the present study was to comprehensively explore the potential adverse effects of TCEP on fish growth and the possible underlying mechanisms. To this end, juvenile yellow catfish (Pelteobagrus fulvidraco) were exposed to environmentally relevant concentrations of TCEP (0, 1, 10 and 100 µg/L) for 30 days. The results showed that exposure to high concentrations of TCEP (10 and 100 µg/L) significantly decreased body weight, body length and specific growth rate (SGR). Plasma IGF-I levels and hepatic mRNA levels of igf1 and igf1r were all reduced, while the transcriptional levels of IGFBPs (igfbp2, igfbp3, igfbp5) were significantly up-regulated in the liver of yellow catfish under exposure to 10 and 100 µg/L TCEP. TCEP-induced growth inhibition might be related to somatostatin (SS) signaling system, as evidenced by elevated mRNA transcriptions of ss in brain and its receptors (sstr2, sstr3, sstr5) in liver. In addition, fish exposed to high concentrations of TCEP displayed multiple histological alterations in liver. Taken together, these findings suggested that TCEP (>10 µg/L) might exert its inhibitory effect on fish growth through interfering with the GH/IGF axis and SS signaling system, and by impairing hepatic structures.

Exposure to diclofenac alters thyroid hormone levels and transcription of genes involved in the hypothalamic-pituitary-thyroid axis in zebrafish embryos/larvae.

Diclofenac (DCF), one of typical non-steroidal anti-inflammatory drugs (NSAIDs), has been frequently detected in various environmental media. Nevertheless，the potential endocrine disrupting effects of DCF on fish were poorly understood. In the present study, zebrafish embryos/larvae were used as a model to evaluate the adverse effects of DCF on development and thyroid system. The results demonstrated that DCF only significantly decreased the heart rate at 72 h post-fertilization (hpf), exhibiting limited influence on the embryonic development of zebrafish. Treatment with DCF significantly reduced whole-body thyroxine (T4) levels, and changed transcriptional levels of several genes related to the hypothalamic-pituitary-thyroid (HPT) axis. These findings provide important information regarding to the mechanisms of DCF-induced developmental toxicity and thyroid disruption in fish.

Comparative transcriptome analysis reveals immunotoxicology induced by three organic UV filters in Manila clam (Ruditapes philippinarum).

Benzophenone-3 (BP-3), 4-methyl-benzylidene camphor (4-MBC) and 2-ethyl-hexyl-4-trimethoxycinnamate (EHMC) are commonly used organic ultraviolet (UV) filters and are frequently detected in water environments. In the present study, we studied the potential adverse impacts of UV filter exposures in Ruditapes philippinarum by investigating transcriptomic profiles and non-specific immune enzyme activities. Transcriptome analysis showed that more genes were differentially regulated in EHMC-treated group, and down-regulated genes (2009) were significantly more than up-regulated ones (410) at day 7. Function annotation revealed that pathways "immune system", "cell growth and death" and "infectious diseases" were significantly enriched. Generally, combined qPCR and biochemical analyses demonstrated that short-term exposure to low dose of UV filters could activate immune responses, whereas the immune system would be restrained after prolonged exposure. Taken together, the present study firstly demonstrated the immunotoxicology induced by BP-3, 4-MBC and EHMC on R. philippinarum, indicating their potential threats to the survival of marine bivalves.

Comparison of fleroxacin oxidation by chlorine and chlorine dioxide: Kinetics, mechanism and halogenated DBPs formation.

Fleroxacin (FLE) is a widely used fluoroquinolones to cure urinary tract infections and respiratory disease, which has been frequently detected in the aquatic environment. The reactivity kinetics of FLE by chlorine and chlorine dioxide (ClO2) and transformation mechanism were investigated in this study. The results showed that FLE was degraded efficiently by chlorine and ClO2, and both reactions followed second-order kinetics overall. The increase of disinfectant dosage and temperature would enhance the degradation of FLE. The highest removal of FLE by chlorine was achieved at a neutral condition (pH 7.4), whereas ClO2 reaction rates increased dramatically with the increasing pH in this study condition. The number of intermediates identified in FLE chlorination and ClO2 oxidation was seven and ten, respectively. The piperazine ring cleavage was the principal and initial reaction in both above reactions. Then, the removal of the piperazine group was predominantly in FLE removal by chlorine, while the decarboxylation mainly occurred in FLE removal by ClO2. The intermediates increased first and then decreased with time, while three kinds of halogenated DBPs increased with time, indicating the above-identified intermediates were further transformed to the halogenated DBPs. Additionally, compared to chlorine reaction, the reaction of ClO2 with FLE reduced the formation of halogenated DBPs, but it also induced the formation of chlorite. The analysis of toxicity showed that compared with chlorination, the oxidation of ClO2 was more suitable for FLE removal.