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The aim of this study was to develop an environmental-benign bio-measure that could be used to purify dye-contaminated wastewater. Herein, a hybrid adsorption-periphyton reactor (HAPR), combining a bioadsorbent based adsorption unit and a periphyton-based photo-bioreactor (PPBR), was built and applied for the first time. Firstly, an efficient bioadsorbent, i.e, microwave-activated swede rape hull (MSRH), was produced, characterized and applied in an adsorption column, to pretreat methylene blue (MB) wastewater with high concentration (~100 mg L -1 or higher). Thereafter, the effluent of adsorption column, with lower dye concentration (~0.5 mg L -1 ), was collected and further purified by PPBR. Results showed that dye removal efficiency by HAPR was 99.95% (from 200 mg L -1 to 0.1 mg L -1 or lower). Decolorization mechanisms by PPBR, included adsorption process by extracellular polymeric substances (EPS) on the surface of periphyton and degradation process. The study showed that HAPR was a novel, environmental friendly, efficient and promising dye-purification method and deserved further attention in future investigation.

In this study, a simple and low-cost method to synthesize iron(III) oxide nanopowders in large quantity was successfully developed for the photocatalytic degradation of microcystin-LR (MC-LR). Two visible light-active iron(III) oxide samples (MG-9 calcined at 200 °C for 5 h and MG-11 calcined at 180 °C for 16 h) with a particle size of 5-20 nm were prepared via thermal decomposition of ferrous oxalate dihydrate in air without any other modifications such as doping. The synthesized samples were characterized by X-ray powder diffraction, 57 Fe Mössbauer spectroscopy, transmission electron microscopy, Brunauer-Emmett-Teller (BET) specific surface area analysis, and UV-visible diffuse reflectance spectroscopy. The samples exhibited similar phase composition (a mixture of α-Fe 2 O 3 and γ-Fe 2 O 3 ), particle size distribution (5-20 nm), particle morphology, and degree of agglomeration, but different specific surface areas (234 m 2  g -1 for MG-9 and 207 m 2  g -1 for MG-11). The results confirmed higher photocatalytic activity of the catalyst with higher specific surface area. The highest photocatalytic activity of the sample to decompose MC-LR was observed at solution pH of 3.0 and catalyst loading of 0.5 g L -1 due to large amount of MC-LR adsorption, but a little iron dissolution of 0.0065 wt% was observed. However, no iron leaching was observed at pH 5.8 even though the overall MC-LR removal was slightly lower than at pH 3.0. Thus, the pH 5.8 could be an appropriate operating condition for the catalyst to avoid problems of iron contamination by the catalyst. Moreover, magnetic behavior of γ-Fe 2 O 3 gives a possibility for an easy separation of the catalyst particles after their use.

The study is aimed at evaluating TiO 2 -SnS 2 composites as effective solar-active photocatalysts for water treatment. Two strategies for the preparation of TiO 2 -SnS 2 composites were examined: (i) in-situ chemical synthesis followed by immobilization on glass plates and (ii) binding of two components (TiO 2 and SnS 2 ) within the immobilization step. The as-prepared TiO 2 -SnS 2 composites and their sole components (TiO 2 or SnS 2 ) were inspected for composition, crystallinity, and morphology using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX) analyses. Diffuse reflectance spectroscopy (DRS) was used to determine band gaps of immobilized TiO 2 -SnS 2 and to establish the changes in comparison to respective sole components. The activity of immobilized TiO 2 -SnS 2 composites was tested for the removal of diclofenac (DCF) in aqueous solution under simulated solar irradiation and compared with that of single component photocatalysts. In situ chemical synthesis yielded materials of high crystallinity, while their morphology and composition strongly depended on synthesis conditions applied. TiO 2 -SnS 2 composites exhibited higher activity toward DCF removal and conversion in comparison to their sole components at acidic pH, while only in situ synthesized TiO 2 -SnS 2 composites showed higher activity at neutral pH.

Metal sulfides are promising photocatalysts for efficient removal of organic pollutants in wastewater. However, the practical application of these catalysts is limited due to the fast recombination of charge carriers and poor catalyst stability. In this study, ternary reduced graphene oxide/SnS 2 /ZnFe 2 O 4 (rGO/SnS 2 /ZnFe 2 O 4 ) composites were synthesized by a hydrothermal process, and rGO content was optimized. The surface morphology, crystal structure, optical and electrochemical properties of rGO/SnS 2 /ZnFe 2 O 4 composites were characterized. The adsorption capacity and visible-light photocatalytic activity of rGO/SnS 2 /ZnFe 2 O 4 were influenced by rGO content with results revealing an optimal rGO content of 7wt.%. The 7% rGO/SnS 2 /ZnFe 2 O 4 composite demonstrated the highest visible-light photocatalytic activity with almost 100% 2-nitrophenol removal, which could be attributed to the efficient charge separation, and the formation of O 2 - , h + and a few OH radicals. The possible photocatalytic mechanism of rGO/SnS 2 /ZnFe 2 O 4 composites was also provided based on the role of rGO and the energy bands of SnS 2 and ZnFe 2 O 4 . Moreover, rGO/SnS 2 /ZnFe 2 O 4 composites exhibit excellent reusability without an obvious decline in the photocatalytic activity after four degradation-regeneration cycles. The results indicate that ternary rGO/SnS 2 /ZnFe 2 O 4 composites have good prospect in practical removal of organic pollutants in wastewater due to high efficiency and excellent stability., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Second-order rate constants [Formula: see text] for the reaction of sulfate radical anion (SO 4 •- ) with trace organic contaminants (TrOCs) are of scientific and practical importance for assessing their environmental fate and removal efficiency in water treatment systems. Here, we developed a chemical structure-based model for predicting [Formula: see text] using 32 molecular fragment descriptors, as this type of model provides a quick estimate at low computational cost. The model was constructed using the multiple linear regression (MLR) and artificial neural network (ANN) methods. The MLR method yielded adequate fit for the training set (R training 2 =0.88,n=75) and reasonable predictability for the validation set (R validation 2 =0.62,n=38). In contrast, the ANN method produced a more statistical robustness but rather poor predictability (R training 2 =0.99andR validation 2 =0.42). The reaction mechanisms of SO 4 •- reactivity with TrOCs were elucidated. Our result shows that the coefficients of functional groups reflect their electron donating/withdrawing characters. For example, electron donating groups typically exhibit positive coefficients, indicating enhanced SO 4 •- reactivity. Electron withdrawing groups exhibit negative values, indicating reduced reactivity. With its quick and accurate features, we applied this structure-based model to 55 discrete TrOCs culled from the Contaminant Candidate List 4, and quantitatively compared their removal efficiency with SO 4 •- and OH in the presence of environmental matrices. This high-throughput model helps prioritize TrOCs that are persistent to SO 4 •- based oxidation technologies at the screening level, and provide diagnostics of SO 4 •- reaction mechanisms., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

A novel magnetically recoverable, visible light active TiO 2 -WO 3 composite (Fe 3 O 4 @SiO 2 @TiO 2 -WO 3 ) was prepared to enable the photocatalyst recovery after the degradation of bisphenol A (BPA) under simulated solar light. For comparison, the photocatalytic activity of other materials such as non-magnetic TiO 2 -WO 3 , Fe 3 O 4 @SiO 2 @TiO 2 , TiO 2 , and the commercial TiO 2 P25 was also evaluated under the studied experimental conditions. The structure and morphology of the synthesized materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and electron dispersion spectroscopy (EDS). Moreover, Brunauer-Emmett-Teller (BET) surface area and magnetic properties of the samples were determined. The Fe 3 O 4 @SiO 2 @TiO 2 -WO 3 and TiO 2 -WO 3 led to a BPA degradation of 17.50 and 27.92 %, respectively, after 2 h of the simulated solar light irradiation. Even though their activity was lower than that of P25, which degraded completely BPA after 1 h, our catalysts were magnetically separable for their further reuse in the treatment. Furthermore, the influence of the water matrix in the photocatalytic activity of the samples was studied in municipal wastewater. Finally, the identification of reaction intermediates was performed and a possible BPA degradation pathway was proposed to provide a better understanding of the degradation process. Graphical abstract ᅟ.

TiO₂ photocatalysis is considered as an alternative to conventional disinfection processes for the inactivation of waterborne microorganisms. The efficiency of photocatalysis is limited by charge carrier recombination rates. When the photocatalyst is immobilized on an electrically conducting support, one may assist charge separation by the application of an external electrical bias. The aim of this work was to study electrochemically assisted photocatalysis with nitrogen doped titania photoanodes under visible and UV-visible irradiation for the inactivation of Escherichia coli . Aligned TiO₂ nanotubes were synthesized (TiO₂-NT) by anodizing Ti foil. Nanoparticulate titania films were made on Ti foil by electrophoretic coating (P25 TiO₂). N-doped titania nanotubes and N,F co-doped titania films were also prepared with the aim of extending the active spectrum into the visible. Electrochemically assisted photocatalysis gave higher disinfection efficiency in comparison to photocatalysis (electrode at open circuit) for all materials tested. It is proposed that electrostatic attraction of negatively charged bacteria to the positively biased photoanodes leads to the enhancement observed. The N-doped TiO₂ nanotube electrode gave the most efficient electrochemically assisted photocatalytic inactivation of bacteria under UV-Vis irradiation but no inactivation of bacteria was observed under visible only irradiation. The visible light photocurrent was only a fraction (2%) of the UV response.

Photodegradation is an important abiotic pathway transforming organic pollutants in natural waters. Humic substances (HS), including humic and fulvic acids, are capable of accelerating the photodegradation of steroid estrogens. However, how the photodegradtion of the emerging pollutants influenced by HS is not clear. Thus, we studied the roles and mechanisms of HS in inducing the photodegradation of 17α-ethynylestradiol (EE2). HS generally induces EE2 photodegradation through binding and reactive species generation. Apart from hydroxyl radical (HO), the excited triplets of humic substances ( 3 HS*) are other key reactive species degrading EE2 by abstracting electrons. HO and 3 HS* were responsible for about 60% of the overall EE2 photodegradation at 250μmol HS L -1 . Most of EE2 molecules bound to the HS via H-bonding, π-π and hydrophobic interactions. The binding role of HS in promoting EE2 photodegradation was rationalized by 17β-estradiol competitive binding with EE2 to the humic and fulvic acids. Furthermore, HS-promoted photodegradation can alter EE2 toxicity to wheat, rice and Ormosia plants. This study extends our knowledge on the photochemical behaviors and ecological risks of steroid estrogens in natural waters., (Copyright © 2016 Elsevier B.V. All rights reserved.)

BiOCl microspheres with exposed {001} facets have been synthesized through a simple solvothermal method. The adsorption and photocatalytic activities of BiOCl microspheres were evaluated by removal of ibuprofen (IBP) as the model reaction. Parameters including IBP concentration, BiOCl dosage, and inorganic ions were investigated to reveal the role of adsorption in BiOCl-based photocatalysis. We found that the high IBP removal rate by BiOCl is not due to photocatalytic oxidation but to surface adsorption. The combination of ICP/MS, IC, XPS, and FT-IR results directly proved that anion exchange between dissociated IBP and Cl accompanied by the formation of surface complex (O-Bi-OOC-C 12 H 17 ) onto the BiOCl surface is the main adsorption mechanism. In addition, we also demonstrated that organic compounds with carboxyl group (-COOH) such as diclofenac, benzoic acid, and p-phthalic acid can be adsorbed by BiOCl while organic compounds without carboxyl group such as carbamazepine, nitrobenzene, and p-chloronitrobenzene cannot be adsorbed. We believe that the BiOCl adsorption behavior and mechanism should be considered when discussing its photocatalytic mechanism.

The interest in using Flue Gas Desulfurization Gypsum (FGDG) for land applications has increased recently. This study evaluates the leaching characteristics of trace elements in "modern" FGDG (produced after fly ash removal) and FGDG-mixed soil (SF) under different environmental conditions using recently approved EPA leaching methods (1313-1316). These methods employ various pH and liquid-solid (LS) ratios under batch leaching, column percolation and diffusion controlled release scenarios. Toxicity Characteristic Leaching Protocol (TCLP) and Synthetic Precipitation Leaching Protocol (SPLP) were used for comparison. The data obtained from new EPA methods provide broad insight into constituent release from FGDG and SF when compared to TCLP and SPLP. The release of toxic elements such as Hg, As, Pb, Co, Cd and Cr from SF was negligible. High release of B from FGDG was observed under all tested conditions; however, its release from SF was low. Both FGDG and SF released Se under all pH conditions (2-13) and LS ratios (1-10) in low concentrations (0.02-0.2mg/L). The data from this study could be used to investigate potential use of "modern" FGDG for new beneficial land applications., (Published by Elsevier B.V.)

Carbon nanotubes (CNTs) have been incorporated into numerous consumer products, and have also been employed in various industrial areas because of their extraordinary properties. The large scale production and wide applications of CNTs make their release into the environment a major concern. Therefore, it is crucial to determine the degree of potential CNT contamination in the environment, which requires a sensitive and accurate technique for selectively detecting and quantifying CNTs in environmental matrices. In this study, a simple device based on utilizing heat generated/temperature increase from CNTs under microwave irradiation was built to quantify single-walled CNTs (SWCNTs), multi-walled CNTs (MWCNTs) and carboxylated CNTs (MWCNT-COOH) in three environmentally relevant matrices (sand, soil and sludge). Linear temperature vs CNT mass relationships were developed for the three environmental matrices spiked with known amounts of different types of CNTs that were then irradiated in a microwave at low energies (70-149W) for a short time (15-30s). MWCNTs had a greater microwave response in terms of heat generated/temperature increase than SWCNTs and MWCNT-COOH. An evaluation of microwave behavior of different carbonaceous materials showed that the microwave measurements of CNTs were not affected even with an excess of other organic, inorganic carbon or carbon based nanomaterials (fullerene, granular activated carbon and graphene oxide), mainly because microwave selectively heats materials such as CNTs that have a higher dielectric loss factor. Quantification limits using this technique for the sand, soil and sludge were determined as low as 18.61, 27.92, 814.4μg/g for MWCNTs at a microwave power of 133W and exposure time of 15s., (Published by Elsevier B.V.)

Nanocrystalline ZnO photocatalysts were prepared by a sol-gel method and modified with fluorine to improve their photocatalytic anti-bacterial activity in visible light. Pathogenic bacteria such as Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) were employed to evaluate the antimicrobial properties of synthesized materials. The interaction with biological systems was assessed by analysis of the antibacterial properties of bacteria suspended in 2% (w/w) powder solutions. The F-doping was found to be effective against S. aureus (99.99% antibacterial activity) and E. coli (99.87% antibacterial activity) when irradiated with visible light. Production of reactive oxygen species is one of the major factors that negatively impact bacterial growth. In addition, the nanosize of the ZnO particles can also be toxic to microorganisms. The small size and high surface-to-volume ratio of the ZnO nanoparticles are believed to play a role in enhancing antimicrobial activity., (Copyright © 2015 Elsevier B.V. All rights reserved.)

In this study, we firstly develop the photo-Fenton-like system with millimetric sponge iron (s-Fe 0 ), H 2 O 2 , visible light (vis, λ≥420nm) and rhodamine B (RhB), and present a comprehensive study concerning the mechanism. Thus, we investigate (1) the adsorption of RhB onto s-Fe 0 , (2) the photo-Fenton-like removal of RhB over iron oxides generated from the corrosion of s-Fe 0 , (3) the homogeneous photo-Fenton removal of RhB over Fe 2+ or Fe 3+ , (4) the Fe 3+ -RhB complexes, and (5) the photo-Fenton-like removal of tetrabromobisphenol A (TBBPA). The results show that neither the adsorption process over s-Fe 0 nor the photo-Fenton-like process over FeOOH, Fe 3 O 4 and Fe 2 O 3 , achieved efficient removal of RhB. For comparison, in homogeneous photo-Fenton process, the presence of Fe 3+ ions, rather than Fe 2+ ions, effectively eliminated RhB. Furthermore, the UV-vis spectra showing new absorbance at∼285nm indicate the complexes of RhB and Fe 3+ ions, adopting vis photons to form excited state and further eject one electron via ligand-to-metal charge-transfer to activate H 2 O 2 . Additionally, efficient TBBPA removal was obtained only in the presence of RhB. Accordingly, the s-Fe 0 - based photo-Fenton-like process assisted with dyestuff wastewater is promising for removing a series of persistent organic pollutants., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Iodinated pharmaceuticals, thyroxine (a thyroid hormone) and diatrizoate (an iodinated X-ray contrast medium), are among the most prescribed active pharmaceutical ingredients. Both of them have been reported to potentially disrupt thyroid homeostasis even at very low concentrations. In this study, UV-254 nm-based photolysis and photochemical processes, i.e., UV only, UV/H 2 O 2 , and UV/S 2 O 8 2- , were evaluated for the destruction of these two pharmaceuticals. Approximately 40% of 0.5μM thyroxine or diatrizoate was degraded through direct photolysis at UV fluence of 160mJcm -2 , probably resulting from the photosensitive cleavage of C-I bonds. While the addition of H 2 O 2 only accelerated the degradation efficiency to a low degree, the destruction rates of both chemicals were significantly enhanced in the UV/S 2 O 8 2- system, suggesting the potential vulnerability of the iodinated chemicals toward UV/S 2 O 8 2- treatment. Such efficient destruction also occurred in the presence of radical scavengers when biologically treated wastewater samples were used as reaction matrices. The effects of initial oxidant concentrations, solution pH, as well as the presence of natural organic matter (humic acid or fulvic acid) and alkalinity were also investigated in this study. These results provide insights for the removal of iodinated pharmaceuticals in water and/or wastewater using UV-based photochemical processes., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Efficient microconcentration of aerosols to a substrate is essential for effectively coupling the collected particles to microscale optical spectroscopies such as laser-induced or spark microplasma, or micro-Raman or infrared spectroscopies. In this study, we present detailed characterization of a corona-based aerosol microconcentration technique developed previously (Diwakar and Kulkarni, 2012). The method involves two coaxial electrodes separated by a few millimeters, one held at a high electrical potential and the other grounded. The particles are collected on the collection (i.e., ground) electrode from a coaxial aerosol flow in a one-step charge-and-collect scheme using corona discharge and electrical precipitation between the two electrodes. Performance of the corona microconcentration method was determined experimentally by measuring collection efficiency, wall losses, and particle deposition density. An intrinsic spectroscopic sensitivity was experimentally determined for the aerosol microconcentrator. Using this sensitivity, we show that corona-based microconcentration is much superior to alternative methods, including filtration, focused impaction using aerodynamic lens, and spot collection using condensational growth. The method offers unique advantages for compact, hand-held aerosol analytical instrumentation.

This paper critically reviews the multidimensional benefits of ozonation in wastewater treatment plants. These benefits include sludge reduction, removal of emerging trace organic contaminants (TrOC) from wastewater and sludge, and resource recovery from sludge. Literature shows that ozonation leads to sludge solubilisation, reducing overall biomass yield. Sludge solubilisation is primarily influenced by ozone dosage, which, in turn, depends on the fraction of ozonated sludge, ozone concentration, and sludge concentration. Additionally, sludge ozonation facilitates the removal of TrOCs from wastewater. On the other hand, by inducing cell lysis, ozonation increases the chemical oxygen demand (COD) and nutrient concentration of the sludge supernatant, which deteriorates effluent quality. This issue can be resolved by implementing resource recovery. Thus far, successful retrieval of phosphorous from ozonated sludge supernatant has been performed. The recovery of phosphorous and other resources from sludge could help offset the operation cost of ozonation, and give greater incentive for wastewater treatment plants to adapt this approach., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Dissolved humic acid (HA) is ubiquitous in natural waters. Its presence significantly changes the photo-and bio-degradation of some organic pollutants in natural waters. The effects of photobleaching on the composition, photosensitizing property and bioavailability of HA were investigated here along with the subsequent influence on its photochemical and biological reactivity in mediating 17α-ethynylestradiol (EE2) degradation. Photobleaching transformed the refractory HA into some small molecules, including organic acids and aliphatics. Along with composition alteration, the photochemical reactivity of HA towards EE2 was slightly depressed, with 9% of the removal rate inhibited by a 70-h photobleaching. Contrarily, the reactivity of HA in mediating EE2 biodegradation by E. coli was significantly promoted by a short-term photobleaching. Compared to the biodegradation of EE2 in the pristine HA, the 10-h photobleached HA increased the biodegradation removal rate of EE2 by 25%, reaching its peak value of about 60%. However, the EE2 biodegradation was inhibited by further irradiation, and the removal rate of EE2 decreased to that in the pristine HA systems. Because no substrate competition was found between EE2 and formate or glucose, EE2 biodegradation mediated by HA in natural waters may not be affected by coexistent organics. Photodegradation and biodegradation of EE2 mediated by HA thus can be combined together by photobleaching to remove pollutants from natural waters. The results reported here could assist environmental risk assessment with respect to EE2 in natural aquatic systems., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

This is the first study to evaluate the potential application of FGDG as an in situ Pb stabilizer in contaminated soils with two different compositions and to explain the underlying mechanisms. A smelter Pb contaminated soil (SM-soil), rich in ferrihydrite bound Pb (FH-Pb), cerussite and litharge with a total Pb content of 65,123mg/kg and an organic matter rich orchard soil (BO-soil), rich in FH-Pb and humic acid bound Pb with a total Pb content of 1532mg/kg were amended with 5% FGDG (w/w). We subjected the two soils to three leaching tests; toxicity characteristic leaching protocol (TCLP), synthetic precipitation leaching protocol (SPLP), kinetic batch leaching test (KBLT) and in-vitro bioaccessibility assay (IVBA) in order to evaluate the FGDG amendment on Pb stabilization. Solid residues of original and FGDG amended soil were analyzed using X-ray absorption spectroscopy (XAS) to identify changes in Pb speciation after each leaching test. The leachate Pb concentrations of FGDG amended soil were lower compared to those of in non-amended soil. The linear combination fitting analysis of XAS confirmed the formation of anglesite and leadhillite in FGDG amended soil. FGDG reduced the Pb desorption from ferrihydrite (FH), by forming FH-Pb-SO 4 ternary complexes. FGDG decreased the Pb adsorption onto humic acid (HA) possibly due to the release of divalent cations such as Ca and Mg, which can compete with Pb to get adsorbed onto HA. The FGDG can successfully be used to remediate Pb contaminated soil. The efficiency of the treatment highly depends on the soil composition., (Published by Elsevier B.V.)

Although UV-induced TiO 2 photocatalysis involves the generation of several reactive oxygen species (ROS), the formation of hydroxyl radicals are generally associated with the degradation of persistent organic contaminants in water. In this study, a variety of radical scavengers were employed to discriminate the roles of different ROS during visible light activated (VLA) photocatalysis using nitrogen and fluorine doped TiO 2 (NF-TiO 2 ) in the degradation of the hepatotoxin, microcystin-LR (MC-LR) in water. The addition of hydroxyl radical scavengers, methanol and tert -butyl alcohol to the reaction mixture resulted in negligible inhibition of VLA NF-TiO 2 photocatalytic degradation of MCLR at pH 3.0 and only partial inhibition at pH 5.7. While hydroxyl radicals generally play the primary role in UV TiO 2 photocatalysis, the minimal influence of MeOH and t-BuOH on the degradation process under these experimental conditions indicates hydroxyl radicals ( • OH) do not play the primary role in VLA NF-TiO 2 photocatalysis. However, strong inhibition was observed in VLA NF-TiO 2 photocatalytic degradation of MC-LR in the presence of superoxide dismutase, benzoquinone and catalase at pH 3.0 and 5.7 indicating O 2 •- and H 2 O 2 play critical roles in the degradation process. Similar degradation rates were observed in the presence of singlet oxygen scavenger, deuterium oxide, which enhances singlet oxygen mediated processes further suggesting singlet oxygen does not play a key role in the degradation of MCLR in these system. Formic acid and cupric nitrate were added to probe the roles of the valence band holes and conduction band electrons, respectively. Under UV+vis light irradiation, almost complete inhibition of MC-LR removal is observed with NF-TiO 2 in the presence of • OH scavengers at pH 5.7. These results demonstrate that solution pH plays a major role in the formation and reactivities of ROS during VLA NF-TiO 2 photocatalysis. The adsorption strength of the scavengers and MCLR onto NF-TiO 2 as well as the speciation of the ROS as a function of pH need to be carefully considered since they also play a key role in the efficiency of the process. These results indicate the reduction of molecular oxygen by photo-generated electrons rather than hydroxyl radicals produced by oxidative reactions of photo-generated holes play a key role in the of VLA NF-TiO 2 photocatalytic degradation of MC-LR.

A heterogeneous manganese/magnetite/graphene oxide (Mn-MGO) hybrid catalyst was fabricated through the reduction of KMnO 4 by ethylene glycol in the presence of magnetite/GO (MGO) particles. The Mn-MGO catalyst exhibited high efficacy and long-term stability in activating peroxymonosulfate (PMS) to generate sulfate radicals for the removal of bisphenol A (BPA) from water. The results of the batch experiments indicated that an increase in the catalyst dose and solution pH could enhance BPA degradation in the coupled Mn-MGO/PMS system. Regardless of the initial pH, the solution pH significantly dropped after the reaction, which was caused by catalytic PMS activation. The production of sulfate radicals and hydroxyl radicals was validated through radical quenching and electron paramagnetic resonances (EPR) tests. BPA degradation pathways were proposed on the basis of LC-MS and GC-MS analyses. Finally, a possible mechanism of catalytic PMS activation was proposed that involved electron transfer from MnO or Mn 2 O 3 to PMS with the generation of sulfate radicals, protons and MnO 2 , as well as the simultaneous reduction of MnO 2 by PMS., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Degradation of dibuytl phthalate (DBP), a plasticizer and also a widely distributed endocrine disruptor, by UV-254 nm/H 2 O 2 advanced oxidation process (AOP) was investigated in this study. A significant DBP removal of 77.1 % at an initial concentration of 1.0 μM was achieved at UV fluence of 160 mJ/cm 2 , initial H 2 O 2 dosage of 1.0 mM, and pH of 7.6 ± 0.1. The DBP degradation exhibited a pseudo-first-order reaction kinetic pattern, with the rate constants linearly increasing with increasing H 2 O 2 dosage while decreasing with increasing initial DBP concentration and pH value in a specific range. DBP destruction was significantly inhibited in the presence of alkalinity and natural organic matter (NOM), two known factors that should be taken a serious consideration of in the research and design of UV/H 2 O 2 -based AOPs. Presence of common inorganic anions (i.e., Cl - , SO 4 2- , and NO 3 - ) and metal cations (i.e., Fe 3+ and Zn 2+ ) had a slight impact on the degradation of DBP, although Cu 2+ could improve the degradation efficiency even at a concentration as low as 0.01 mg/L, suggesting a strong potential of applying UV/H 2 O 2 for the removal of DBP with an environmental relevant level of copper.

Toxins produced by cyanobacteria in freshwater ecosystems constitute a serious health risk worldwide for humans that may use the affected water bodies for recreation, drinking water, and/or irrigation. Cyanotoxins have also been deemed responsible for loss of animal life in many places around the world. This paper explores the effect of H 2 O 2 treatments on cyanobacteria and microcystins in natural samples from a hypertrophic reservoir in microcosm experiments. According to the results, cyanobacteria were more easily affected by H 2 O 2 than by other phytoplanktonic groups. This was shown by the increase in the fractions of chlorophyll-a (a proxy for phytoplankton) and chlorophyll-b (a proxy for green algae) over total phytoplankton pigments and the decrease in the fraction of phycocyanin (a proxy for cyanobacteria) over total phytoplankton pigments. Thus, while an overall increase in phytoplankton occurred, a preferential decrease in cyanobacteria was observed with H 2 O 2 treatments over a few hours. Moreover, significant degradation of total microcystins was observed under H 2 O 2 treatments, while more microcystins were degraded when UV radiation was used in combination with H 2 O 2 . The combination of H 2 O 2 and ultraviolet (UV) treatment in natural samples resulted in total microcystin concentrations that were below the World Health Organization limit for safe consumption of drinking water of 1 μg/L. Although further investigation into the effects of H 2 O 2 addition on ecosystem function must be performed, our results show that the application of H 2 O 2 could be a promising method for the degradation of microcystins in reservoirs and the reduction of public health risks related to the occurrence of harmful algal blooms.

The United States Environmental Protection Agency Contaminant Candidate List 3 lists strontium as a contaminant for potential regulatory consideration in drinking water. Very limited data is available on strontium removal from drinking water and as a result, there is an immediate need for treatment information. The objective of this work is to evaluate the effectiveness of coagulation/filtration and lime-soda ash softening treatment methods to remove strontium from surface and ground waters. Coagulation/filtration jar test results on natural waters showed that conventional treatment with aluminum and iron coagulants were able to achieve only 12% and 5.9% strontium removal, while lime softening removed as high as 78% from natural strontium-containing ground water. Controlled batch experiments on synthetic water showed that strontium removal during the lime-soda ash softening was affected by pH, calcium concentration and dissolved inorganic carbon concentration. In all softening jar tests, the final strontium concentration was directly related to the initial strontium concentration and the removal of strontium was directly associated with calcium removal. Precipitated solids showed well-formed crystals or agglomerates of mixed solids, two polymorphs of calcium carbonate (vaterite and calcite), and strontianite, depending on initial water quality conditions. X-ray diffraction analysis suggested that strontium was likely incorporated in the calcium carbonate crystal lattice and was likely responsible for removal during lime softening., (Copyright © 2016. Published by Elsevier Ltd.)

In this study, persulfate (PS) activation by nano-Fe(0) was used to degrade dichlorodiphenyltrichloroethane (DDT), and the mechanism of this process was elucidated with EPR, GC-MS and free-radical quenching studies. It was found that DDT was degraded efficiently in PS/nano-Fe(0), and GC-MS analysis showed that benzoic acid, benzyl alcohol, dichlorobenzophenone and 2,2-bis(p-chlorophenyl)-ethane were the dominant products of DDT degradation, while only dechlorination products (DDD and DDE) were observed in nano-Fe(0) without persulfate. EPR results showed that persulfate activation by nano-Fe(0) led to the production of more sulfate radicals and hydroxyl radicals, which accounted for DDT degradation. But the free radical quenching studies suggested that the addition of ethanol to PS/nano-Fe(0) favored the reductive dechlorination of DDT, which was ascribed that the formed ethanol radical (CH(CH3)OH) enhanced the reductive dechlorination of DDT. Furthermore, the nano-Fe(0) loading not only affected the degradation efficiency of DDT, but also influenced the intermediate product distribution of DDT degradation in the PS/nano-Fe(0) process., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The study is aimed at evaluating the potential of immobilized TiO2-based zeolite composite for solar-driven photocatalytic water treatment. In that purpose, TiO2-iron-exchanged zeolite (FeZ) composite was prepared using commercial Aeroxide TiO2 P25 and iron-exchanged zeolite of ZSM5 type, FeZ. The activity of TiO2-FeZ, immobilized on glass support, was evaluated under solar irradiation for removal of diclofenac (DCF) in water. TiO2-FeZ immobilized in a form of thin film was characterized for its morphology, structure, and composition using scanning electron microscopy/energy-dispersive x-ray spectroscopy (SEM/EDX). Diffuse reflectance spectroscopy (DRS) was used to determine potential changes in band gaps of prepared TiO2-FeZ in comparison to pure TiO2. The influence of pH, concentration of hydrogen peroxide, FeZ wt% within the composite, and photocatalyst dosage on DCF removal and conversion efficiency by solar/TiO2-FeZ/H2O2 process was investigated. TiO2-FeZ demonstrated higher photocatalytic activity than pure TiO2 under solar irradiation in acidic conditions and presence of H2O2.

Owing to their atomically thin structure, large surface area and mechanical strength, 2D nanoporous materials are considered to be suitable alternatives for existing desalination and water purification membrane materials. Recent progress in the development of nanoporous graphene based materials has generated enormous potential for water purification technologies. Progress in the development of nanoporous graphene and graphene oxide (GO) membranes, the mechanism of graphene molecular sieve action, structural design, hydrophilic nature, mechanical strength and antifouling properties and the principal challenges associated with nanopore generation are discussed in detail. Subsequently, the recent applications and performance of newly developed 2D materials such as 2D boron nitride (BN) nanosheets, graphyne, molybdenum disulfide (MoS2), tungsten chalcogenides (WS2) and titanium carbide (Ti3C2Tx) are highlighted. In addition, the challenges affecting 2D nanostructures for water purification are highlighted and their applications in the water purification industry are discussed. Though only a few 2D materials have been explored so far for water treatment applications, this emerging field of research is set to attract a great deal of attention in the near future.

A sensitive, field-portable microplasma spectroscopy method has been developed for real-time measurement of carbon nanomaterials. The method involves microconcentration of aerosol on a microelectrode tip for subsequent analysis for atomic carbon using laser-induced breakdown spectroscopy (LIBS) or spark emission spectroscopy (SES). The spark-induced microplasma was characterized by measuring the excitation temperature (15,000 - 35,000 K), electron density (1.0 × 10 17 - 2.2 × 10 17 cm -3 ), and spectral responses as functions of time and interelectrode distance. The system was calibrated and detection limits were determined for total atomic carbon (TAC) using a carbon emission line at 247.856 nm (C I) for various carbonaceous materials including sucrose, EDTA, caffeine, sodium carbonate, carbon black, and carbon nanotubes. The limit of detection for total atomic carbon was 1.61 ng, equivalent to 238 ng m -3 when sampling at 1.5 L min -1 for 5 min. To improve the selectivity for carbon nanomaterials, which consist of elemental carbon (EC), the cathode was heated to 300 °C to reduce the contribution of organic carbon to the total atomic carbon. Measurements of carbon nanotube aerosol at elevated electrode temperature showed improved selectivity to elemental carbon and compared well with the measurements from thermal optical method (NIOSH Method 5040). The study shows that the SES method to be an excellent candidate for development as a low-cost, hand-portable, real-time instrument for measurement of carbonaceous aerosols and nanomaterials.

Zinc oxide (ZnO)-coated zeolite adsorbents were developed by both nitric acid modification and Zn(NO3)2·6H2O functionalization of zeolite 4A. The developed adsorbents were used for the removal of humic acid (HA) from aqueous solutions. The synthesized materials were characterized by porosimetry analysis, scanning electron microscopy, X-Ray diffraction analysis, and high resolution transmission electron microscopy. The maximum adsorption capacity of the adsorbents at 21±1°C was about 60mgCg(-1). The results showed that the positive charge density of ZnO-coated zeolite adsorbents was proportional to the amount of ZnO coated on zeolite and thus, ZnO-coated zeolite adsorbents exhibited a greater affinity for negatively charged ions. Furthermore, the adsorption capacity of ZnO-coated zeolite adsorbents increased markedly after acid modification. Adsorption experiments demonstrated ZnO-coated zeolite adsorbents possessed high adsorption capacity to remove HA from aqueous solutions mainly due to strong electrostatic interactions between negative functional groups of HA and the positive charges of ZnO-coated zeolite adsorbents., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A series of Ag2S-Ag2CO3 (4%, 8%, 16%, 32% and 40% Ag2S), Ag2CO3@Ag2S (32%Ag2S) and Ag2S@Ag2CO3 (32%Ag2S) composite photocatalysts were fabricated by coprecipitation or successive precipitation reaction. The obtained catalysts were analyzed by N2 physical adsorption, powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, UV-vis diffuse reflectance spectroscopy and photocurrent test. Under visible light irradiation, the influences of Ag2S content and core-shell property on photocatalytic activity and stability were evaluated in studies focused on the degradation of methyl orange (MO) dye, phenol, and bisphenol A. Results showed that excellent photocatalytic performance was obtained over Ag2S/Ag2CO3 composite photocatalysts with respect to Ag2S and Ag2CO3. With optimal content of Ag2S (32 wt%), the Ag2S-Ag2CO3 showed the highest photocatalytic degradation efficiency. Moreover, the structured property of Ag2S/Ag2CO3 greatly influenced the activity. Compared with Ag2S-Ag2CO3 and Ag2CO3@Ag2S, core-shell like Ag2S@Ag2CO3 demonstrated the highest activity and stability. The main reason for the boosting of photocatalytic performance was due to the formation of Ag2S/Ag2CO3 well contacted interface and unique electron structures. Ag2S/Ag2CO3 interface could significantly increase the separation efficiency of the photo-generated electrons (e(-)) and holes (h(+)), and production of OH radicals. More importantly, the low solubility of Ag2S shell could effectively protect the core of Ag2CO3, which further guarantees the stability of Ag2CO3., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

In UV-254 nm/H2O2 advanced oxidation process (AOP), the potential degradation pathways for organic pollutants include (1) hydrolysis, (2) direct H2O2 oxidation, (3) UV direct photolysis, and (4) hydroxyl radical (HO(•)) reaction. In this study, the contribution of these pathways was quantitatively assessed in the photochemical destruction of 4-chlorophenol (4-CP), demonstrating pathways (3) and (4) to be predominantly responsible for the removal of 4-CP by UV/H2O2 in 50 mM phosphate buffer solution. Increasing reaction pH could significantly enhance the contribution of direct photolysis in UV/H2O2 process. The contribution of HO(•) oxidation was improved with increasing initial H2O2 concentration probably due to the increased formation of HO(•). Presence of sodium carbonate (Na2CO3) as in UV/H2O2/Na2CO3 system promoted the degradation of 4-CP, with carbonate radical (CO3 (•-)) reaction and direct photolysis identified to be the main contributing pathways. The trends in the contribution of each factor were further evaluated and validated on the degradation of the antibiotic compound oxytetracycline (OTC). This study provides valuable information on the relative importance of different reaction pathways on the photochemical degradation of organic contaminants such as 4-CP and OTC in the presence and absence of a CO3 (•-) precursor.

In this study, a new catalytic degradation technology using microwave induced carbon nanotubes (MW/CNTs) was proposed and applied in the treatment of organic pollutants in aqueous solution. The catalytic activity of three CNTs of 10-20nm, 20-40nm, and 40-60nm diameters were compared. The results showed that organic pollutants such as methyl orange (MO), methyl parathion (MP), sodium dodecyl benzene sulfonate (SDBS), bisphenol A (BPA), and methylene blue (MB) in aqueous solution could be degraded effectively and rapidly in MW/CNTs system. CNTs with diameter of 10-20nm exhibited the highest catalytic activity of the three CNTs under MW irradiation. Further, complete degradation was obtained using 10-20nm CNTs within 7.0min irradiation when 25mL MO solution (25mg/L), 1.2g/L catalyst dose, 450W, 2450MHz, and pH=6.0 were applied. The rate constants (k) for the degradation of SDBS, MB, MP, MO and BPA using 10-20nm CNTs/MW system were 0.726, 0.679, 0.463, 0.334 and 0.168min(-1), respectively. Therefore, this technology may have potential application for the treatment of targeted organic pollutants in wastewaters., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this study, mesoporous iron/aluminum (Fe/Al) bimetallic particles were synthesized and employed for the removal of aqueous As(III). Scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS), Brunauer-Emmett-Teller (BET) analysis method, Vibrating-sample magnetometry (VSM), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR) were employed to characterize the Fe/Al bimetals before and after reaction with As(III). The physical properties, compositions, and structures of Fe/Al bimetallic particles as well as the As(III) removal mechanism were investigated. The characterization of the bimetallic particles after the reaction has revealed the removal of As(III) is a complex process including surface adsorption and oxidation, and intraparticle reduction. The good As(III) removal capability and stability of the Fe/Al bimetallic particles exhibited its great potential as an effective and environmental friendly agent for As(III) removal from water., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

TiO2-encapsulated H-ZSM photocatalysts were prepared by physical mixing of TiO2 and zeolites. Pt was immobilized on the surface of the TiO2-encapsulated zeolite (H-ZSM) catalysts by a simple photochemical reduction method. Different weight ratios of both TiO2 and Pt were hybridized with H-ZSM and the catalytic performance of the prepared catalysts was investigated for 2-propanol oxidation in liquid phase and acetaldehyde in gas phase reaction. Around 5-10 wt% TiO2-encapsulated H-ZSM catalysts was found to be optimal amount for the effective oxidation of the organics. Prior to light irradiation, Pt-TiO2-H-ZSM showed considerable amount of catalytic degradation of 2-propanol in the dark, forming acetone as an intermediate. In this study, Pt has played a major and important role on the total oxidation of 2-propanol as well as acetaldehyde. As a result, no residual organics were present in the pores of the zeolites. The catalysts could be reused more than three times without losing their catalytic activity in both phases. The Pt-TiO2-H-ZSM photocatalysts could overcome the problem of strong adsorption of organics in the zeolite pores (after the reaction). Thus, Pt-TiO2-H-ZSM can be used as a potential catalyst for both liquid and gas phase oxidation of organic pollutants., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Contaminated soil and water pose a serious threat to human health and ecosystem. For the treatment of industrial effluents or minimizing their detrimental effects, preventive and remedial approaches must be adopted prior to the occurrence of any severe environmental, health, or safety hazard. Conventional treatment methods of wastewater are insufficient, complicated, and expensive. Therefore, a method that could use environmentally friendly surfactants for the simultaneous removal of both organic and inorganic contaminants from wastewater is deemed a smart approach. Surfactants containing potential donor ligands can coordinate with metal ions, and thus such compounds can be used for the removal of toxic metals and organometallic compounds from aqueous systems. Surfactants form host-guest complexes with the hydrophobic contaminants of water and soil by a mechanism involving the encapsulation of hydrophobes into the self-assembled aggregates (micelles) of surfactants. However, because undefined amounts of surfactants may be released into the aqueous systems, attention must be paid to their own environmental risks as well. Moreover, surfactant remediation methods must be carefully analyzed in the laboratory before field implementation. The use of biosurfactants is the best choice for the removal of water toxins as such surfactants are associated with the characteristics of biodegradability, versatility, recovery, and reuse. This Review is focused on the currently employed surfactant-based soil and wastewater treatment technologies owing to their critical role in the implementation of certain solutions for controlling pollution level, which is necessary to protect human health and ensure the quality standard of the aquatic environment.

Carbonate radical (CO3(•-)), a selective oxidant, reacts readily with electron-rich compounds through electron transfer and/or hydrogen abstraction. In this study, the role of CO3(•-) in degrading oxytetracycline (OTC) by UV only, UV/H2O2 and UV/persulfate (UV/PS) advanced oxidation processes (AOPs) in the presence of HCO3(-) or CO3(2-) was investigated. For UV only process, the presence of photosensitizers, i.e., nitrate (NO3(-)) and natural organic matter (NOM), had different impacts on OTC degradation, i.e., an enhancing effect by NO3(-) due to the generation of HO(•) and a slight inhibiting effect by NOM possibly due to a light scattering effect. Differently for UV/H2O2 and UV/PS processes, the presence of NO3(-) hardly influenced the destruction of OTC. Generation of CO3(•-) presented a positive role on OTC degradation by UV/NO3(-)/HCO3(-). Such influence was also observed in the two studied AOPs in the presence of both bicarbonate and other natural water constituents. When various natural water samples from different sources were used as reaction matrices, UV only and UV/H2O2 showed an inhibiting effect while UV/PS demonstrated a comparable or even promoting effect in OTC decomposition. After elucidating the potential contribution of UV direct photolysis via excited state OTC* at an elevated reaction pH condition, putative OTC transformation byproducts via CO3(•-) reaction were identified by ultra-high definition accurate-mass quadrupole time-of-flight tandem mass spectrometry (QTOF/MS). Five different reaction pathways were subsequently proposed, including hydroxylation (+16 Da), quinonization (+14 Da), demethylation (-14 Da), decarbonylation (-28 Da) and dehydration (-18 Da). The significant role of UV at high pH and CO3(•-) on OTC removal from contaminated water was therefore demonstrated both kinetically and mechanistically., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Blooms of toxic cyanobacteria in water supply systems are a global issue affecting water supplies on every major continent except Antarctica. The occurrence of toxic cyanobacteria in freshwater is increasing in both frequency and distribution. The protection of water supplies has therefore become increasingly more challenging. To reduce the risk from toxic cyanobacterial blooms in drinking water, a multi-barrier approach is needed, consisting of prevention, source control, treatment optimization, and monitoring. In this paper, current research on some of the critical elements of this multi-barrier approach are reviewed and synthesized, with an emphasis on the effectiveness of water treatment technologies for removing cyanobacteria and related toxic compounds. This paper synthesizes and updates a number of previous review articles on various aspects of this multi-barrier approach in order to provide a holistic resource for researchers, water managers and engineers, as well as water treatment plant operators., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Background: Antiangiogenic agents have been recently added to the oncological armamentarium with bevacizumab probably being the most popular representative in current clinical practice. The elucidation of the mode of action of these agents is a prerequisite for personalized prediction of antiangiogenic treatment response and selection of patients who may benefit from this kind of therapy. To this end, having used as a basis a preexisting continuous vascular tumour growth model which addresses the targeted nature of antiangiogenic treatment, we present a paper characterized by the following three features. First, the integration of a two-compartmental bevacizumab specific pharmacokinetic module into the core of the aforementioned preexisting model. Second, its mathematical modification in order to reproduce the asymptotic behaviour of tumour volume in the theoretical case of a total destruction of tumour neovasculature. Third, the exploitation of a range of published animal datasets pertaining to antitumour efficacy of bevacizumab on various tumour types (breast, lung, head and neck, colon)., Results: Results for both the unperturbed growth and the treatment module reveal qualitative similarities with experimental observations establishing the biologically acceptable behaviour of the model. The dynamics of the untreated tumour has been studied via a parameter analysis, revealing the role of each relevant input parameter to tumour evolution. The combined effect of endogenous proangiogenic and antiangiogenic factors on the angiogenic potential of a tumour is also studied, in order to capture the dynamics of molecular competition between the two key-players of tumoural angiogenesis. The adopted methodology also allows accounting for the newly recognized direct antitumour effect of the specific agent., Conclusions: Interesting observations have been made, suggesting a potential size-dependent tumour response to different treatment modalities and determining the relative timing of cytotoxic versus antiangiogenic agents administration. Insight into the comparative effectiveness of different antiangiogenic treatment strategies is revealed. The results of a series of in vivo experiments in mice bearing diverse types of tumours (breast, lung, head and neck, colon) and treated with bevacizumab are successfully reproduced, supporting thus the validity of the underlying model.

Oxytetracycline (OTC), an important broad-spectrum antibiotic, has been detected extensively in various environmental systems, which may have a detrimental impact on ecosystem and human health through the development of drug resistant bacteria and pathogens. In this study, the degradation of OTC was evaluated by UV-254nm activated persulfate (PS). The observed UV fluence based pseudo first-order rate constant (kobs) was found to be the highest at near neutral pH conditions (pH 5.5-8.5). Presence of various natural water constituents had different effects on OTC degradation, with a significant enhancement in the presence of bicarbonate or Cu(2+). Limited elimination of total organic carbon (TOC) and PS was observed during the mineralization of OTC. Transformation byproducts in the presence and absence of hydroxyl radical scavenging agent tert-butanol (t-BuOH) were identified using ultra-high definition accurate-mass quadrupole time-of-flight liquid chromatography/mass spectrometer (LC-QTOF/MS). Potential OTC degradation mechanism was subsequently proposed revealing four different reaction pathways by SO4(-) reaction including hydroxylation (+16Da), demethylation (-14Da), decarbonylation (-28Da) and dehydration (-18Da). This study suggests that UV-254nm/PS is a promising treatment technology for the control of water pollution caused by emerging contaminants such as OTC., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Visible light (VIS) photocatalysis has large potential as a sustainable water treatment process, however the reaction pathways and degradation processes of organic pollutants are not yet clearly defined. The presence of cyanobacteria cause water quality problems since several genera can produce potent cyanotoxins, harmful to human health. In addition, cyanobacteria produce taste and odor compounds, which pose serious aesthetic problems in drinking water. Although photocatalytic degradation of cyanotoxins and taste and odor compounds have been reported under UV-A light in the presence of TiO2, limited studies have been reported on their degradation pathways by VIS photocatalysis of these problematic compounds. The main objectives of this work were to study the VIS photocatalytic degradation process, define the reactive oxygen species (ROS) involved and elucidate the reaction mechanisms. We report carbon doped TiO2 (C-TiO2) under VIS leads to the slow degradation of cyanotoxins, microcystin-LR (MC-LR) and cylindrospermopsin (CYN), while taste and odor compounds, geosmin and 2-methylisoborneol, were not appreciably degraded. Further studies were carried-out employing several specific radical scavengers (potassium bromide, isopropyl alcohol, sodium azide, superoxide dismutase and catalase) and probes (coumarin) to assess the role of different ROS (hydroxyl radical OH, singlet oxygen (1)O2, superoxide radical anion [Formula: see text] ) in the degradation processes. Reaction pathways of MC-LR and CYN were defined through identification and monitoring of intermediates using liquid chromatography tandem mass spectrometry (LC-MS/MS) for VIS in comparison with UV-A photocatalytic treatment. The effects of scavengers and probes on the degradation process under VIS, as well as the differences in product distributions under VIS and UV-A, suggested that the main species in VIS photocatalysis is [Formula: see text] , with OH and (1)O2 playing minor roles in the degradation., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A series of two-dimensional (2D) interlaced BiOCl/carbon quantum dot composites (denoted as BiOCl/CQD composites) were synthesized by a template-free coprecipitation method at room temperature, and the influence of different particle size distributions of the CQDs on the physiochemical properties and photocatalytic activities of the BiOCl/CQD composites was studied. CQDs can change the morphology and increase the specific surface area of the BiOCl/CQD composites. Moreover, the particle size distribution of the CQDs (CQD loading amount) has some effect on the light absorption, separation of photogenerated charge carriers, and photocatalytic performance of  the BiOCl/CQD composites. The optimized size distribution of the CQDs is 50-150 nm. BiOCl/CQD (50-150 nm) composites showed the best improvement of light absorption and the highest photocurrent density of 0.44 μA cm(-2), and exhibited the highest photocatalytic activity with almost 100% 2-nitrophenol removal under visible-light irradiation. The high efficacy of BiOCl/CQD (50-150 nm) composites could be attributed to their excellent light absorption and highly effective separation of photogenerated charge carriers.

Cylindrospermopsin (CYN) is a potent toxic alkaloid produced by a number of cyanobacteria frequently found in lakes and reservoirs used as drinking water sources. We report for the first time detailed pathways for the degradation of CYN by treatment with ozone. This was accomplished by use of ultra-high-performance liquid chromatography (UHPLC)-quadrupole time-of-flight mass spectrometry (QTOF MS), which revealed that CYN is readily degraded by ozone with at least 36 transformation products. Structural similarities among the major products indicated that the carbon-carbon double bond in the uracil ring of CYN was most susceptible to attack by ozone. Furthermore, the nitrogen functionality associated with the tricyclic guanidine moiety is also involved via a degradation pathway that has not been previously observed. To assess the potential toxicity of ozonation products of CYN, the cytotoxicity of CYN and the mixture of its ozonation products was measured in a human hepatoma cell line (HepG2). The IC50 for CYN at 24 and 48 h incubations was approximately 64.1 and 12.5 μM, respectively; however, the ozonation products of CYN did not exhibit measurable cytotoxicity to human cells. The results indicate ozone is an effective and practical method for CYN attenuation in water treatment without formation of overtly toxic transformation products.

To enhance the dechlorination reactivity of millimetric sponge iron (s-Fe(0)), a facile one-pot method was used to decorate s-Fe(0) with Ag(+) ions under ambient conditions. The results recorded by X-ray diffraction patterns, X-ray photoelectron spectra and high-resolution transmission electron microscopy demonstrated that the growth of Ag(0) was dominated primarily by (111) plane with a mean length of ∼20 nm. The roles of Ag(0) loading, catalyst dosage, particle size, initial pH and contaminant concentration were assessed during the removal of pentachlorophenol (PCP). Catalyst recyclability was also studied. The results revealed that 3-5mm s-Fe(0) particles with 5 wt% Ag(0) loading exhibited the best performance with a dose of 3.0 g per 60 mL PCP solution. In addition, the dechlorination of PCP followed two-step, pseudo-first-order reaction kinetics, and Ag(0)-s-Fe(0) was advantageous compared with bimetals of nanoscale zero-valent iron, iron power and iron flakes. The dechlorination mechanism of PCP over Ag(0)-s-Fe(0) was attributed to the surface Ag(0) decoration, which catalyzed the formation of reactive hydrogen atoms for indirect reaction, and the direct electron transfer via Fe-Ag(0) galvanic cells for direct reaction. This suggests that Ag-based bimetals of s-Fe(0) have great potential in the pretreatment of organic halogen compounds in aqueous solution., (Copyright © 2015 Elsevier B.V. All rights reserved.)

This study evaluates the feasibility of UV-C-driven advanced oxidation process induced by sulfate radicals SO4(.)- in degrading erythromycin (ERY) in secondary treated wastewater. The results revealed that 10 mg L(-1) of sodium persulfate (SPS) can result in rapid and complete antibiotic degradation within 90 min of irradiation, while ERY decay exhibited a pseudo-first-order kinetics pattern under the different experimental conditions applied. ERY degradation rate was strongly affected by the chemical composition of the aqueous matrix and it decreased in the order of: ultrapure water (kapp = 0.55 min(-1)) > bottled water (kapp = 0.26 min(-1)) > humic acid solution (kapp = 0.05 min(-1)) > wastewater effluents (kapp = 0.03 min(-1)). Inherent pH conditions (i.e. pH 8) yielded an increased ERY degradation rate, compared to that observed at pH 3 and 5. The contribution of hydroxyl and sulfate radicals (HO. and SO4(.)-) on ERY degradation was found to be ca. 37% and 63%, respectively. Seven transformation products (TPs) were tentatively elucidated during ERY oxidation, with the 14-membered lactone ring of the ERY molecule being intact in all cases. The observed phytotoxicity against the tested plant species can potentially be attributed to the dissolved effluent organic matter (dEfOM) present in wastewater effluents and its associated-oxidation products and not to the TPs generated from the oxidation of ERY. This study evidences the potential use of the UV-C/SPS process in producing a final treated effluent with lower phytotoxicity (<10%) compared to the untreated wastewater. Finally, under the optimum experimental conditions, the UV-C/SPS process resulted in total inactivation of ERY-resistant Escherichia coli within 90 min., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The iron/aluminum (Fe/Al) bimetallic particles with high efficiency for the removal of Cr(VI) were prepared. Fe/Al bimetallic particles were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), SEM mapping, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). SEM mapping showed that the core of bimetal was Al, and the planting Fe was deposited on the surface of Al. In acidic and neutral conditions, Fe/Al bimetal can completely remove Cr(VI) from wastewater in 20 min. Even at pH 11.0, the Cr(VI) removal efficiency achieved was 93.5%. Galvanic cell effect and high specific surface area are the main reasons for the enhanced removal of Cr(VI) by bimetallic particles. There were no iron ions released in solutions at pH values ranging from 3.0 to 11.0. The released Al(3+) ions concentrations in acidic and neutral conditions were all less than 0.2mg/L. The bimetal can be used 4 times without losing activity at initial pH 3.0. XPS indicated that the removed Cr(VI) was immobilized via the formation of Cr(III) hydroxide and Cr(III)-Fe(III) hydroxide/oxyhydroxide on the surface of Fe/Al bimetal. The Fe/Al bimetallic particles are promising for further testing for the rapid and effective removal of contaminants from water., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Bromate formation in bromide-containing water through the cobalt (Co)-mediated activation of peroxymonosulfate (PMS) was investigated. Increasing the PMS dosage and the cobalt dosage increased the formation of bromate and bromate yields of up to 100% were recorded under the test conditions. The bromate yield increased to a maximum as the pH rose from 2.7 to 6 before decreasing by over 90% as the pH rose further from 6 to above 9. The bromate formation is a two-step process involving free bromine as a key intermediate and bromate as the final product. In the first step, apart from the known oxidation of bromide to free bromine and of free bromine to bromate by sulfate radicals (SO4(-)), Co(III) produced from the oxidation of Co(II) by PMS and SO4(-) also oxidizes bromide to free bromine. The contribution of Co(III) to the bromate formation was verified with the addition of methanol and EDTA, a radical scavenger and a Co(III) ligand, respectively. In the presence of methanol, free bromine formation increased with increasing Co(II) dosage but no bromate was detected, indicating that Co(III) oxidized bromide to form free bromine but not bromate. In the presence of both EDTA and methanol, no free bromine or bromate was detected, as Co(III) was stabilized by EDTA to form the Co(III)EDTA(-) complex, which could not oxidize bromide. Mathematical simulation further suggested that Co(III) outweighed SO4(-) to oxidize bromide to free bromine. On the other hand, SO4(-) is essential for the oxidation of free bromine to bromate in the second step. In real water, the presence of NOM significantly decreased the bromate formation but caused the brominated organic DBP formation with high quantity. This is the first study to demonstrate the significant bromate formation in the Co/PMS system and the substantial contribution of Co(III) to the formation., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

One of the main goals of organic chemists is to find easy, environmentally friendly, and cost effective methods for the synthesis of industrially important compounds. Photocatalysts have brought revolution in this regard as they make use of unlimited source of energy (the solar light) to carry out the synthesis of organic compounds having otherwise complex synthetic procedures. However, selectivity of the products has been a major issue since the beginning of photocatalysis. The present article encompasses state of the art accomplishments in harvesting light energy for selective organic transformations using photocatalysts. Several approaches for the development of photocatalysts for selective organic conversions have been critically discussed with the objective of developing efficient, selective, environmental friendly and high yield photocatalytic methodologies., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Diffused sunlight is found to be an effective light source for the efficient degradation and mineralization of organic pollutant (methyl orange as a probe) by sono-photocatalytic degradation using reduced graphene oxide (rGO) supported CuO-TiO2 photocatalyst. The prepared catalysts are characterized by XRD, XPS, UV-vis DRS, PL, photoelectrochemical, SEM-EDS and TEM. A 10 fold synergy is achieved for the first time by combining sonochemical and photocatalytic degradation under diffused sunlight. rGO loading augments the activity of bare CuO-TiO2 more than two fold. The ability of rGO in storing, transferring, and shuttling electrons at the heterojunction between TiO2 and CuO facilitates the separation of photogenerated electron-hole pairs, as evidenced by the photoluminescence results. The complete mineralization of MO and the by-products within a short span of time is confirmed by TOC analysis. Further, hydroxyl radical mediated degradation under diffused sunlight is confirmed by LC-MS. This system shows similar activity for the degradation of methylene blue and 4-chlorophenol indicating the versatility of the catalyst for the degradation of various pollutants. This investigation is likely to open new possibilities for the development of highly efficient diffused sunlight driven TiO2 based photocatalysts for the complete mineralization of organic contaminants., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Wastewater reuse is currently considered globally as the most critical element of sustainable water management. The dissolved effluent organic matter (dEfOM) present in biologically treated urban wastewater, consists of a heterogeneous mixture of refractory organic compounds with diverse structures and varying origin, including dissolved natural organic matter, soluble microbial products, endocrine disrupting compounds, pharmaceuticals and personal care products residues, disinfection by-products, metabolites/transformation products and others, which can reach the aquatic environment through discharge and reuse applications. dEfOM constitutes the major fraction of the effluent organic matter (EfOM) and due to its chemical complexity, it is necessary to utilize a battery of complementary techniques to adequately describe its structural and functional character. dEfOM has been shown to exhibit contrasting effects towards various aquatic organisms. It decreases metal uptake, thus potentially reducing their bioavailability to exposed organisms. On the other hand, dEfOM can be adsorbed on cell membranes inducing toxic effects. This review paper evaluates the performance of various advanced treatment processes (i.e., membrane filtration and separation processes, activated carbon adsorption, ion-exchange resin process, and advanced chemical oxidation processes) in removing dEfOM from wastewater effluents. In general, the literature findings reveal that dEfOM removal by advanced treatment processes depends on the type and the amount of organic compounds present in the aqueous matrix, as well as the operational parameters and the removal mechanisms taking place during the application of each treatment technology., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study investigated the effects of metals (Fe3+, Cu2+, Ni2+, and Zn2+) and phenolic compounds (PCs: hydroquinone, catechol, and phenol) loaded on biomass on the formation of persistent free radicals (PFRs) in biochar. It was found that metal and phenolic compound treatments not only increased the concentrations of PFRs in biochar but also changed the types of PFRs formed, which indicated that manipulating the amount of metals and PCs in biomass may be an efficient method to regulate PFRs in biochar. These results provided direct evidence to elucidate the mechanism of PFR formation in biochar. Furthermore, the catalytic ability of biochar toward persulfate activation for the degradation of contaminants was evaluated. The results indicated that biochar activates persulfate to produce sulfate radicals (SO4•-) and degraded polychlorinated biphenyls (PCBs) efficiently. It was found that both the concentration and type of PFRs were the dominant factors controlling the activation of persulfate by biochar and that superoxide radical anions account for 20-30% of sulfate radical generation in biochar/persulfate. This conclusion was supported by linear correlations between the concentration of PFRs consumed and the formation of SO4•- and between λ (λ=[formed sulfate radicals]/[consumed PFRs]) and g-factors. The findings of this study provide new methods to manipulate PFR concentration in biochar for the transformation of contaminants and development of new alternative activators for persulfate-based remediation of contaminated soils.