Silver microspheres coated with a molecularly imprinted polymer as a SERS substrate for sensitive detection of bisphenol A.

An efficient approach is demonstrated for preparing particles consisting of a silver core and a shell of molecularly imprinted polymer (Ag@MIP). The MIP is prepared by using bisphenol A (BPA) as the template and 4-vinylpyridine as the functional monomer. The Ag@MIP fulfills a dual function in that the silver core acts as a SERS substrate, while the MIP allows for selective recognition of BPA. The Ag@MIP is characterized by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, thermogravimetric analysis and Raman spectroscopy. The Raman intensity of Ag@MIP is higher than that of bare silver microspheres. The detection limit for BPA is as low as 10-9 mol·L-1. Graphical abstract Schematic illustration of the preparation of silver microspheres coated with a molecularly imprinted polymer (Ag@MIPs) for detecting bisphenol A (BPA) by surface enhanced Raman scattering (SERS).

A Ag-molecularly imprinted polymer composite for efficient surface-enhanced Raman scattering activities under a low-energy laser.

In this work, we have fabricated flower-shaped Ag particles coated with a molecularly imprinted polymer (Ag@MIP) based on the molecular imprinting technique and SERS technology. Although Raman signals decrease with the reducing laser power, Ag@MIP could sensitively detect the target molecules even at a laser power as low as 0.14 µW. As a new SERS substrate, Ag@MIP shows high enhancement under low irradiation effectively, which limits the possible laser induced effects in the measurement process, improving the signal-to-noise ratio and repeatability. This platform has potential for the development of next-generation SERS spectroscopy.

Anti-VEGFR2-Interferon α Promotes the Infiltration of CD8+ T Cells in Colorectal Cancer by Upregulating the Expression of CCL5.

SUMMARY: Immunocytokines are a promising immunotherapeutic approach in cancer therapy. Anti-VEGFR2-interferon α (IFNα) suppressed colorectal cancer (CRC) growth and enhanced CD8 + T-cell infiltration in the tumor microenvironment, exhibiting great clinical translational potential. However, the mechanism of how the anti-VEGFR2-IFNα recruits T cells has not been elucidated. Here, we demonstrated that anti-VEGFR2-IFNα suppressed CRC metastasis and enhanced CD8 + T-cell infiltration. RNA sequencing revealed a transcriptional activation of CCL5 in metastatic CRC cells, which was correlated with T-cell infiltration. IFNα but not anti-VEGFR2 could further upregulate CCL5 in tumors. In immunocompetent mice, both IFNα and anti-VEGFR2-IFNα increased the subset of tumor-infiltrating CD8 + T cells through upregulation of CCL5. Knocking down CCL5 in tumor cells attenuated the infiltration of CD8 + T cells and dampened the antitumor efficacy of anti-VEGFR2-IFNα treatment. We, therefore, propose upregulation of CCL5 is a key to enhance infiltration of CD8 + T cells in metastatic CRC with IFNα and IFNα-based immunocytokine treatments. These findings may help the development of IFNα related immune cytokines for the treatment of less infiltrated tumors.

Elementary photoelectronic processes at a porphyrin dye/single-walled TiO2 nanotube hetero-interface in dye-sensitized solar cells: a first-principles study.

A unique one-dimensional (1D) sandwich single-walled TiO2 nanotube (STNT) is proposed as a photoanode nanomaterial with perfect morphology and large specific surface area. We have thoroughly examined the elementary photoelectronic processes occurring at the porphyrin dye/STNT hetero-interface in dye-sensitized solar cells (DSSCs) by theoretical simulation. It is desirable to investigate the interfacial photoelectronic processes to elucidate the electron transfer and transport mechanism in 1D STNT-based DSSCs. We have found that the photoexcitation and interfacial charge separation mechanism can be described as follows. A ground-state electron of the dye molecule (localized around the electron donor) is first promoted to the excited state (distributed electron donor), and then undergoes ultrafast injection into the conduction band of the STNT, leaving a hole around the oxidized dye. Significantly, the injected electron in the conduction band is transported along the STNT by means of Ti 3d (x2-y2) orbitals, offering a unidirectional electron pathway toward the electrode for massive collection without the observation of trap states. Our study not only provides theoretical guidelines for the modification of TiO2 nanotubes as a photoanode material, but also opens a new perspective for the development of a novel class of TiO2 nanotubes with high power-generation efficiency.

Graphitic carbon nitride membranes intercalated with nano-sized Fe-MOF for enhanced water purification via synergistic separation and Fenton-like processes.

Versatile two-dimensional nanomaterials have offered a promising prospect to enhance the water purification efficiency and overcome the fouling obstacle in membrane technology. In this work, a graphitic carbon nitride (g-C3N4) nanosheet membrane intercalated with the nano-sized Fe-based metal-organic framework (MIL-100(Fe)) is developed for the enhanced removal of aqueous organic contaminants by synergically promoting separation and Fenton-like processes. The g-C3N4/MIL-100(Fe) membrane is constructed through a self-assembly route in which the nano-MIL-100(Fe) is anchored into g-C3N4 layers by the coordination bonds between Fe nodes and pyridinic N. The MIL-100(Fe) intercalation not only enlarges the interlayer spacing to raise the membrane permeability, but also expedites the electron transfer between Fe2+ and Fe3+ to improve the Fenton-like activity. With a stable water flux of 98.2 L m2·h-1·bar-1 under wide-range pH and pressures, the g-C3N4/MIL-100(Fe) membrane shows high dye removal efficiency (≥99%) and prominent self-cleaning ability. Mechanism insight proposes a combination of size exclusion, electrostatic interaction and steady radical generation. The intercalation of nano-MIL-100(Fe) into g-C3N4 membranes can realize the mutual promotion between separation and Fenton-like processes, the synergistic effect of which provides an effective and feasible strategy for aqueous pollution abatement.

Waste biomass-derived N, P co-doping carbon aerogel-coated CoxFe1-xP with modulated electron density for efficient electrooxidation of contaminants.

Developing low-cost, green, high-performing electrode materials to address environmental pollutants and the energy crisis is significant but challenging. Herein, the bimetallic iron cobalt phosphide coated in waste biomass-derived N, P co-doping carbon (CoxFe1-xP@NPC) is constructed. Furthermore, the active site density and the water decomposition energy barrier of surface-coated NPC are modulated by optimizing the electronic structure of CoxFe1-xP via doping engineering. The Fe-modulated CoxFe1-xP@NPC exhibits a hierarchical porous self-supporting structure and excellent physical & chemical properties with excellent electrooxidation performance, achieving over 95% removal of TCH within 60 min. The density functional theory (DFT) calculations further confirms that N carries more positive charge and P carries more negative charge in the NPC of CoxFe1-xP@NPC with Fe modulation, which can promote the adsorption and dissociation of water molecules. Of note, Co0.75Fe025P@NPC displays a low water dissociation energy barrier to produce ·OH and a high energy barrier to produce O2 than its counterparts. This study offers new insight into controllable modulation of biomass carbon-based composite electrode catalytic activity for high-efficiency degradation of contaminants.

Gravity-driven membrane system treating heavy metals-containing secondary effluent: Improved removal of heavy metals and mechanism.

This study aimed at investigating the removal performance of the gravity-driven membrane (GDM) system in treating the heavy metals-containing secondary effluent, as well as evaluating the respective roles of Fe and Mn addition on the removal of heavy metals. GDM process with the formation of biocake layer exerted effective removals of Cr, Pb and Cd, with an average removal efficiency of 98%, 95% and 40%, respectively, however, after removing the biocake layer, the removal efficiencies of Cr, Pb and Cd reduced to 59%, 85% and 19%, respectively, indicating that the biocake layer played a fundamental role in removing heavy metals. With the assistance of Fe, the removal efficiency of heavy metals increased, and exhibited a positive response to the Fe dosage, due to the adsorption by the freshly generated iron oxides. On the contrary, the Mn involvement would result in the reduction of Cd removal due to the competitive adsorption of residual dissolved Mn2+ and Cd. Furthermore, the addition of a high dosage of Fe increased the diversity of eukaryotic communities and facilitated the elimination of heavy metals, however, the involvement of Mn would lead to a reduction in microbial diversity, resulting in a decrease of heavy metal removal efficiency. These findings are expected to develop new tactics to enhance heavy metal removal and promote widespread application of GDM technology in the fields of deep treatment of heavy metals-containing wastewater and reclamation of secondary effluent.

Comparative study on heterogeneous activation of peroxydisulfate and peroxymonosulfate with black carbon derived from coal tar residues: Contribution of free radical, 1O2 and surface-bound radicals.

Carbon materials draw increasing attention as metal-free catalysts for persulfates activation. Herein, the potential of black carbon (BC) derived from coal tar residues on heterogeneous activation of peroxydisulfate (PDS) and peroxymonosulfate (PMS) to eliminate organic pollutants was investigated. Compared with UV/persulfates systems, persulfates/BC systems degraded 3 selected phenolic compounds (i.e. phenol, 4-chlorophenol (4-CP) and bisphenol A (BPA)) with an order of magnitude higher oxidation rates, and removed dissolved organics (DOC) with over 27% higher efficiency. In the PDS/BC system, 1O2 and surface-bound radicals were proved to be the dominant active species, while free radicals, 1O2, and surface-bound radicals were responsible for organics oxidation in the PMS/BC system. Relative contribution of different reactive species in persulfates/BC systems was pH-dependent. Surface oxygen functionalities of BC were involved in 1O2 generation, and its structural defects played a critical role in forming free radicals and surface-bound radicals. This study provided an in-depth insight into carbon-driven persulfates activation processes.

Insight into the oxidation of phenolic pollutants by enhanced permanganate with biochar: The role of high-valent manganese intermediate species.

This work demonstrated that the oxidation of phenolic pollutants by permanganate (KMnO4) was effectively enhanced by a commercial biochar. Detailed characterization data indicated that the biochar contains porous structures, amounts of defective sites and abundant redox-active groups. In the presence of biochar, the degradation efficiency of 4-nitrophenol by KMnO4 surged from 5% to 92% in 180 min, up to 37.8% of total organic carbon (TOC) was removed. Meanwhile, acute toxicity of 4-nitrophenol was greatly reduced. Through analyzing oxidation products of triclosan (TCS) and using methyl phenyl sulfoxide (PMSO) as a chemical probe, high-valent Mn intermediates (i.e. Mn(VI)/Mn(V)) were proved to be the dominant oxidant in the KMnO4/biochar system. Quantitative structure-activity relationships (QSARs) were established between oxidation rate constants of various substituted phenols and classical descriptor variables (i.e., Hammett constant σ+). KMnO4/biochar was found to be less selective to the substituent variation of phenolic compounds compared with O3, K2FeO4, ClO2 and persulfate/carbon nanotube (PDS/CNT). This work provided a novel catalytic oxidation technology for eliminating phenolic compounds, and improved insights into the mechanistic study of the KMnO4-based oxidation process.

Non-radical dominated degradation of bisphenol S by peroxymonosulfate activation under high salinity condition: Overlooked HOCl, formation of intermediates, and toxicity assessment.

Extensive studies revealed that Cl- could inhibit the removal of targeted pollutants under low Cl- conditions in the peroxymonosulfate (PMS) system. However, the enhanced effect of Cl- has always been overlooked under high Cl- conditions. Here, we find that high concentration of Cl- played a critical role in bisphenol S (BPS) degradation by activating PMS using 16%-CoFe2O4@PAL (16%-CFO@PAL). The removal of BPS was sharply enhanced after introducing 0.5 and 1.0 M Cl-, and the corresponding kobs increased to 0.922 min-1 and 1.103 min-1, which was 6-fold and 7-fold higher than the control (0.144 min-1), respectively. HOCl was demonstrated as the dominant species for removing BPS in 16%-CFO@PAL/PMS system under high Cl- circumstances. The typical chlorinated BPS intermediates were identified, which showed higher eco-toxicity than BPS. The chlorinated byproducts along with their toxicity could be effectively eliminated after 30 min. The possible formation mechanism of chlorinated products was further revealed by theoretical calculations. Toxicity assessment experiments showed that BPS significantly affected hormone levels of zebrafish and showed toxicity on the testis and liver of zebrafish, which could be reduced using 16%-CFO@PAL/PMS system. This study attracts attention to the overlooked HOCl in PMS-based processes under high salinity conditions.

Activation of peroxymonosulfate by palygorskite-mediated cobalt-copper-ferrite nanoparticles for bisphenol S degradation: Influencing factors, pathways and toxicity evaluation.

Peroxymonosulfate (PMS)-based advanced oxidation process is considered a potential technology for water treatment. Here, palygorskite (PAL)-mediated cobalt-copper-ferrite nanoparticles (16%-CoCu0.4Fe1·6O4@PAL, donated as 16%-CCFO@PAL) were employed for PMS activation to remove bisphenol S (BPS). BPS degradation was greater than 99% under the optimal conditions within 25 min, on which the effects of various influencing factors were explored. The adsorption dissociation energy of PMS over 16%-CCFO@PAL was -6.27 eV, which was lower than that of the Cu-free catalyst (-6.15 eV), demonstrating the excellent catalytic ability of 16%-CCFO@PAL. The efficient catalytic ability of 16%-CCFO@PAL was also verified in real water samples. The oxidation intermediates were identified and their generations were systematically analyzed by DFT calculations. The possible degradation pathways of BPS were proposed and the toxicity of products was predicted. BPS affected the normal development of zebrafish embryos and the levels of sex hormone in adult male zebrafish, and was harmful to the tissues, such as testis, liver, and intestine of zebrafish. The 16%-CCFO@PAL/PMS process can effectively reduce the toxicity of BPS-polluted water. This study paves the way for the real application of 16%-CCFO@PAL/PMS oxidation process and provides a new perspective for the evaluation of water toxicity.

Probing the electronic and optical properties of silica-coated quantum dots with first-principles calculations.

The electronic and optical natures of silica-coated semiconductor nanocrystals (Cd(2)Te(2)@(SiO(2))(24)) have been investigated by density functional theory (DFT) and time-dependent DFT calculations. The calculated results of Cd(2)Te(2)@(SiO(2))(24) have revealed that the structural synergy effect between the Cd(2)Te(2) quantum dots (QDs) and the silica coating shell plays a dominant role in the photoelectric properties. The binding of embedded Cd(2)Te(2) to the outer silica coating shell leads to the distortion of the silica nanocage, indicating strong coupling between the QDs and silica shell. The optical features of Cd(2)Te(2) clusters and Cd(2)Te(2)@(SiO(2))(24) complexes were evaluated using the time-dependent DFT method. It is determined that the maximal absorption peak of isolated Cd(2)Te(2) in a UV-Vis absorption spectrum appears at 584 nm, which shifts to 534 nm when the Cd(2)Te(2) QDs were encapsulated by silica, in close agreement with the experimental evidence. The excited process has a direct electronic transition character from the occupied Cd(2)Te(2) states to the outer silica nanocage excited states (core → shell electronic transitions). A deep insight into silica-coated QD systems is beneficial for understanding their optical nature and the development of core/shell QDs.

Heterogeneous catalytic ozonation of atrazine with Mn-loaded and Fe-loaded biochar.

After reaction with permanganate or ferrate, the resulted Mn-loaded and Fe-loaded biochar (MnOx/biochar and FeOx/biochar) exhibited excellent catalytic ozonation activity. O3 (2.5 mg/L) eliminated 48% of atrazine (ATZ, 5 µM) within 30 min at pH 7.0, while under identical conditions, ozonation efficiency of ATZ increased to 83% and 100% in MnOx/biochar and FeOx/biochar (20 mg/L) heterogeneous catalytic systems, respectively. Radical scavenger experiment and electron paramagnetic resonance (EPR) analysis confirmed that hydroxyl radical (•OH) was the dominant oxidant. Total Lewis acid sites on MnOx/biochar and FeOx/biochar were 3.5 and 4.1 times of that on the raw biochar, which induced enhanced adsorption of O3 and its subsequent decomposition into •OH. Electron transfer via redox pairs on MnOx/biochar and FeOx/biochar was observed by cyclic voltammetry scans, which also functioned in the improved catalytic capacity. Degradation pathways of ATZ in MnOx/biochar and FeOx/biochar ozonation systems were proposed, with 34.6% and 44.8% of dechlorination effect accomplished within 30 min of reaction, which was improved by 4.1 and 5.3 times compared to pure ozonation. After 12-hour treatment, acute toxicity of ATZ oxidation products was reduced from 38.3% of pure ozonation system to 14.5% and 6.3% of activated ozonation systems with MnOx/biochar and FeOx/biochar, respectively. Mn-loaded biochar and Fe-loaded biochar have great potential for heterogeneous catalytic ozonation of polluted water.

Bio-inspired co-deposited preparation of GO composite loose nanofiltration membrane for dye contaminated wastewater sustainable treatment.

The fully separation of dye/salt through loose nanofiltration membranes is of great significance for the sustainable development paradigm of textile wastewater. However, the current loose nanofiltration membranes suffer low separation efficiency and complex preparation. Herein, by one-step co-deposition, we develop graphene oxide (GO) composite loose nanofiltration membranes with low negatively charged surface. Our membrane possesses unconventional high pure water permeation of 71.7 LMH/bar, 92.9 % rejection for Methyl blue (MB) and 98.8 % rejection for Congo red (CR). Benefiting from the large interlayer distance of GO nanosheets and low negatively charged surface, membrane achieves high dyes/salts separation with satisfactory permeation to salts (94.3 % of Na2SO4, 97.6 % of MgSO4, 98.3 % of MgCl2 and 99.0 % of NaCl). The CR/salt mixed solutions exhibit similar removal rates to their constituents' single dye or salt solutions (CR rejection is up to more than 97 % and the permeations of all salts are above 93 %). At the same time, binary dyes mixtures (Congo red and Methyl orange) can also be effectively separated. Furthermore, the membrane shows a relatively desirable antifouling property. The flux recovery still remains at 85.9 % after three cycling filtrations. This study provides a facile approach to prepare highly-efficient loose nanofiltration membranes for wastewater sustainable remediation.

Tailoring the distribution of microbial communities and gene expressions to achieve integrating nitrogen transformation in a gravity-driven submerged membrane bioreactor.

A pilot-scale upgraded gravity-driven submerged membrane (GDSM) reactor was constructed to enhance nitrogen removal. It was artificially formed multiple stratified environments (dissolved oxygen (DO) and substrate supply (TOC, TN, COD, NH4+-N, NO2--N, and NO3--N)) by embedding moving water baffles to control water-flow process in bulk liquid with slow-flowing liquid state. Significant diversity and relative abundance of microorganisms associated with nitrogen transformation paths (i.e., ammonia-oxidizing archaea, ammonia-oxidizing bacteria, nitrite oxidizing bacteria, and denitrifying bacteria) were tailored to distribute on different spatial and temporal regions, and performed their dominant functions. The process simultaneously integrated diverse and effective nitrogen transformation paths (i.e., nitrification, partial nitrification, denitrification, anammox, and dissimilatory nitrate reduction) to achieve high nitrogen removal, with NH4+-N, TN, and COD eliminated by 94.68 ± 2.55%, 55.16 ± 5.53%, and 80.17 ± 6.75%, respectively. Gene expressions involved in the nitrogen transformations were estimated by qPCR to explore the shifts of dominant nitrogen transforming bioreactions in multiple stratified environments. Pearson correlation coefficients supported that the functional genes had more stable and active ability by complementing each other. As a result, an endogenous integration of diverse nitrogen transformation paths was achieved in a single system by artificially tailoring the distributions of microbial communities and gene expressions with enhanced nitrogen removal.

Catalytic ozonation of rhodamine B over CuO catalyst confined in multiwalled carbon nanotubes: An experimental and theoretical account.

We first attempted to fill CuO particles in the channel of carbon nanotubes (CNTs) as novel catalytic materials CuO@CNTs used for ozonation of rhodamine B (RhB) in aqueous solution. Catalyst samples were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), thermogravimetry (TG), the Brunauer-Emmett-Teller (BET) surface area method, X-ray photoelectron spectroscopy (XPS), and Fourier transform IR (FT-IR) method. Removal efficiency of RhB was significantly promoted at the presence of ozonation/CuO@CNTs compared with that of ozonation alone, ozonation/pure CNTs, and ozonation with CuO-coating CNTs catalyst (CuO/CNTs). Electron paramagnetic resonance (EPR) experiments, molecular dynamics (MD) simulation, and density functional theory (DFT) calculations further demonstrated that CNTs provided a confined environment to promote the decomposition of ozone and the generation of hydroxyl radical, making the ozonation process more efficient. This study provided a possible treatment approach for organic pollutants by using CNTs-confined nanocatalysts in aqueous solution.

Enhanced mineralization of atrazine by surface induced hydroxyl radicals over light-weight granular mixed-quartz sands with ozone.

A light-weight granular mixed-quartz sand (denoted as L-GQS) combined with stirring-assisted bubble column reactor was firstly applied in catalytic ozonation of atrazine. The L-GQS, with a density of 2.36 g cm-3 and average diameter of ca. of 4 mm, was readily churned up and uniformly distributed within the solution in the reactor. The introduction of L-GQS was found to exhibit enhanced catalytic ozonation of atrazine, with the increase in degradation rate and the dissolved organic carbon (DOC) removal being more than 2-fold for the catalytic process (L-GQS dosage = 5 g L-1, [atrazine]0 = 50 µM, [O3] = 25 mg L-1, gas flow = 0.2 L min-1, at pH 7.0 and 293 K). The L-GQS settled at the bottom of the reactor after experimentation, allowing its easy separation from the solution. A complete characterization of the material (XRD, XPS, FTIR, FE-SEM/EDS, BET and pHpzc) revealed that L-GQS consisted of α-quartz, ß-cristobalite, anorthoclase and small amount of iron oxy-hydroxides. Hydroxyl groups, Bronsted acid sites and Lewis acid sites on the surface of L-GQS all contributed to the atrazine adsorption, ozone decomposition and ·OH generation. The L-GQS catalyzed ozonation exhibited superior atrazine degradation and mineralization rates in a wide range of pH (3.0-9.0) and reaction temperatures (278 K-293 K). Also, an enhancement of DOC abatement was observed both in presence of natural organic matter isolates and natural water matrices (river water) when L-GQS was used. Finally, the degradation mechanism was proposed, based on the intermediates and by-products formation analyzed by LC-QTOF-MS/MS and ionic chromatography. Our results indicate that the L-GQS combined with stirring-assisted bubble column reactor could be utilized as an enhancement of ozone-based advanced oxidation processes.

Morphology Control Studies of MnTiO3 Nanostructures with Exposed {0001} Facets as a High-Performance Catalyst for Water Purification.

Novel single-crystal hexagonal MnTiO3 nanosheets with exposed {0001} facets have been synthesized via a simple one-pot hydrothermal method using NaOH as a mineralizer and tetraethylammonium hydroxide (TEAH) as a morphology controller. The intermediate morphologies of MnTiO3 nanostructures such as nanoparticles, nanowires, nanorods, and nanodiscs are trapped kinetically by adjusting the synthesis conditions. This approach enables us to elucidate the growth mechanisms of MnTiO3 nanosheets based on the tetraethylammonium cation adsorption abilities on different MnTiO3 crystal facets combined with density functional theory calculations. Dissolution and recrystallization processes are involved during the MnTiO3 crystallization. The surface-controlled MnTiO3 has been found to be effective as a catalyst for ozonation in the degradation of 4-chlorophenol (4-CP). Within typical experimental conditions (catalyst dosage = 0.3 g L-1, [4-CP]0 = 50 mg L-1, [O3] = 20 mg L-1, gas flow = 0.1 L min-1, pH 6.8, and T = 293 K), the total organic carbon (TOC) removal efficiency of 4-CP in catalytic ozonation with well-structured MnTiO3 (MnTiO3-180-10 sample) was 76.3% after 60 min, compared with only 22.1 and 38.5% TOC removal in the absence of catalyst and with uncontrolled MnTiO3 (MnTiO3-no TEAH sample), respectively. Benefiting from the high exposure percentage of {0001} facet, mixed-valences of manganese, surface hydroxyl groups, and the enrichment Lewis acid sites provided by Mn and Ti, the morphology-controlled MnTiO3 nanosheets can be applied as heterogeneous catalytic ozonation catalysts which exhibit excellent pollutant degradation. We anticipate that MnTiO3 can be a promising candidate material for the application in remediation of organic pollutants in water.

Development of a novel anoxic/oxic fed-batch membrane bioreactor (AFMBR) based on gravity-driven and partial aeration modes: A pilot scale study.

A novel pilot gravity-driven anoxic/oxic fed-batch membrane bioreactor (AFMBR) was developed to treat real domestic wastewater. In this process, the anoxic and oxic stages created favorable conditions for stable and continuous nitritation-denitritation/denitrification-nitrification links without adding external carbon source. Excellent removals of organic carbon/nitrogen (NH4+-N: 71-97%, COD: 78-96%, UV254: 70-95%, TN: 20-60%) and spontaneous permeability recovery were achieved simultaneously. It was assessed at micro levels by characterizing sludge particle morphologies, microbiota functional evolutions, fouling layer properties and energy consumptions. It was demonstrated that the aerobic granular sludge (AGS) was cultivated successfully. Notable differences of microbial diversity were observed in different regions of AFMBR. The SEM and AFM spectra suggested the loose cake layers can shed automatically due to low pressure and continue flushing. The energy consumption in AFMBR was around 0.042 kWh/m3, far lower than that of conventional MBR. Overall, the AFMBR has a potential on improvement of domestic wastewater treatment.

Rapid oxidation of iodide and hypoiodous acid with ferrate and no formation of iodoform and monoiodoacetic acid in the ferrate/I-/HA system.

Toxic and odorous iodinated disinfection byproducts (I-DBPs) could form in the chemical oxidation of iodine-containing water. A critical step for controlling the hazardous I-DBPs is to convert the iodine species into stable and harmless iodate (IO3-) while inhibiting the accumulation of highly reactive hypoiodous acid (HOI). Herein, the oxidation of I- and HOI with ferrate was investigated, and the formation profile of HOI was determined based on 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) coloring method through a stopped-flow spectrophotometer. The second-order rate constants (kapp) of ferrate with HOI decreased from 1.6 × 105 M-1s-1 to 8.3 × 102 M-1s-1 as the solution pH varied from 5.3 to 10.3, which were 7.5, 7.2 and 13.8 times higher than that of ferrate with I- at pH 6.0, 7.0 and 8.0, respectively. Compared with other oxidants such as ozone, hypochlorous acid, chloramine and potassium permanganate, ferrate would swiftly oxidize HOI formed in the I- oxidation process. For the ferrate oxidation of I-containing water, HOI was swiftly oxidized to IO3- from pH 5.0 to 9.0. Phosphate buffer promoted the oxidation of I- while inhibited the oxidation of HOI with ferrate. When 5 mgC/L of humic acids (HA) existed in the solution, no formation of iodoform and monoiodoacetic acid (MIAA) was observed in the oxidation of iodide (20 µM) with ferrate (from 10 µM to 80 µM). These results suggested that ferrate oxidation could be an effective method for the control of I-DBPs in iodine-containing water treatment.