A new type of Au/TiO2/reduced graphene oxide (RGO) nanocomposite was fabricated by the hydrothermal synthesis of TiO2 on graphene oxide followed by the photodeposition of Au nanoparticles. Transmission electron microscopy images showed that Au nanoparticles were loaded onto the surface of both TiO2 and RGO. Au/TiO2/RGO had a better photocatalytic activity than Au/ TiO2 for the degradation of phenol. Electrochemical measurements indicated that Au/TiO2/RGO had an improved charge transfer capability. Meanwhile, chemiluminescent analysis and electron spin resonance spectroscopy revealed that Au/TiO2/RGO displayed high production of hydrogen peroxide and hydroxyl radicals in the photocatalytic process. This high photocatalytic performance was achieved via the addition of RGO in Au/TiO2/RGO, where RGO served not only as a catalyst support to provide more sites for the deposition of Au nanoparticles but also as a collector to accept electrons from TiO2 to effectively reduce photogenerated charge recombination.
Effect of different carbon sources on purification performance and change of microbial community structure in a novel A2N-MBR process were investigated. The results showed that when fed with acetate, propionate or acetate and propionate mixed (1:1) as carbon sources, the effluent COD, NH4+-N, TN and TP were lower than 30, 5, 15 and 0.5 mg?L–1, respectively. However, taken glucose as carbon source, the TP concentration of effluent reached 2.6 mg?L–1. Process analysis found that the amount of anaerobic phosphorus release would be the key factor to determine the above effectiveness. The acetate was beneficial to the growth of Candidatus Accumulibacter associated with biological phosphorus removal, which was the main cause of high efficiency phosphorus removal in this system. In addition, it could eliminate the Candidatus Competibacter associated with glycogen-accumulating organisms and guarantee high efficiency phosphorus uptake of phosphorus accumulating organisms in the system with acetate as carbon source.
In this study, FeVO4 was prepared and used as Fenton-like catalyst to degrade orange G (OG) dye. The removal of OG in an aqueous solution containing 0.5 g·L–1 FeVO4 and 15 mmol·L–1 hydrogen peroxide at pH 7.0 reached 93.2%. Similar rates were achieved at pH 5.7 (k = 0.0471 min–1), pH 7.0 (k = 0.0438 min–1), and pH 7.7 (k = 0.0434 min–1). The FeVO4 catalyst successfully overcomes the problem faced in the heterogeneous Fenton process, i.e., the narrow working pH range. The data for the removal of OG in FeVO4 systems containing H2O2 conform to the Langmuir–Hinshelwood model (R2 = 0.9988), indicating that adsorption and surface reaction are the two basic mechanisms for OG removal in the FeVO4–H2O2 system. Furthermore, the irradiation of FeVO4 by visible light significantly increases the degradation rate of OG, which is attributed to the enhanced rates of the iron cycles and vanadium cycles.
First-principles calculations were performed to investigate the mechanism of Hg0 adsorption and oxidation on CeO2(111). Surface oxygen activated by the reduction of Ce4+ to Ce3+ was vital to Hg0 adsorption and oxidation processes. Hg0 was fully oxidized by the surface lattice oxygen on CeO2(111), without using any other oxidizing agents. HCl could dissociate and react with the Hg adatom on CeO2(111) to form adsorbed Hg–Cl or Cl–Hg–Cl groups, which promoted the desorption of oxidized Hg and prevented CeO2 catalyst deactivation. In contrast, O–H and H–O–H groups formed during HCl adsorption consumed the active surface oxygen and prohibited Hg oxidation. The consumed surface oxygen was replenished by adding O2 into the flue gas. We proposed that oxidized Hg desorption and maintenance of sufficient active surface oxygen were the rate-determining steps of Hg0 removal on CeO2-based catalysts. We believe that our thorough understanding and new insights into the mechanism of the Hg0 removal process will help provide guidelines for developing novel CeO2-based catalysts and enhance the Hg0 removal efficiency.
Ammonia has emerged as a promising hydrogen carrier with applications as an energy source in recent years. However, in addition to being toxic, gaseous ammonia is a precursor of secondary inorganic aerosols. The concentration of ambient fine particulate matter (PM2.5) is intrinsically connected to public health. In this study, PM2.5-related health impacts of utilizing ammonia-hydrogen energy in Kanto Region, Japan, were investigated. It was assumed that 20% of the electricity consumption in Kanto Region, the most populated area in Japan, was supplied by ammonia-hydrogen energy. The PM2.5 resulted from incomplete ammonia decomposition was simulated by a chemical transport model: ADMER-PRO (modified version). Based on the incremental PM2.5 concentration, health impacts on the elderly (individuals over 65 years old) were quantitatively evaluated. The ammonia emission in this scenario increased PM2.5 by 11.7% (0.16 μg·m–3·y–1) in winter and 3.5% (0.08 μg ·m–3·y–1) in summer, resulting in 351 premature deaths per year. This study suggests that costeffective emissions control or treatment and appropriate land planning should be considered to reduce the associated health impacts of this type of energy generation. In addition, further in-depth research, including cost-benefit analysis and security standards, is needed.
Fe-BEA catalysts are active for the NH3-SCR of NO. For industrial application, a binder should be added to the Fe-BEA catalysts to make them tightly adhere to the monoliths. The addition of alumina and zirconia as binders to the Fe-BEA led to a different effect on NO conversion. The catalytic activity of the mixed samples was evaluated by the temperature programmed procedure in a flow-reactor system, and the mechanism was analyzed via SEM, BET, XRD and XPS. It was found that larger iron particles were formed by the migration of parent iron particles in the Fe-BEA catalyst with alumina. This led to the increase of Fe3+ magnitude and iron cluster, enhancing the abilities of NO oxidation and storage. Accordingly, the SCR activity increased slightly in low temperature but decreased sharply in high temperature. For the Fe-BEA with zirconia sample, NO oxidation and storage abilities decreased due to the less iron clusters. The increase of Fe3+ magnitude resulted in higher catalytic oxidation ability, which gave rise to little change in the SCR activity compared with the Fe-BEA.
We implemented the online coupled WRF-Chem model to reproduce the 2013 January haze event in North China, and evaluated simulated meteorological and chemical fields using multiple observations. The comparisons suggest that temperature and relative humidity (RH) were simulated well (mean biases are–0.2K and 2.7%, respectively), but wind speeds were overestimated (mean bias is 0.5 m?s–1). At the Beijing station, sulfur dioxide (SO2) concentrations were overpredicted and sulfate concentrations were largely underpredicted, which may result from uncertainties in SO2 emissions and missing heterogeneous oxidation in current model. We conducted three parallel experiments to examine the impacts of doubling SO2 emissions and incorporating heterogeneous oxidation of dissolved SO2 by nitrogen dioxide (NO2) on sulfate formation during winter haze. The results suggest that doubling SO2 emissions do not significantly affect sulfate concentrations, but adding heterogeneous oxidation of dissolved SO2 by NO2 substantially improve simulations of sulfate and other inorganic aerosols. Although the enhanced SO2 to sulfate conversion in the HetS (heterogeneous oxidation by NO2) case reduces SO2 concentrations, it is still largely overestimated by the model, indicating the overestimations of SO2 concentrations in the North China Plain (NCP) are mostly due to errors in SO2 emission inventory.
The gene for the catalytic domain of thermostable endo-β-1,3-glucanase (laminarinase) LamA was cloned from Thermotoga maritima MSB8 and heterologously expressed in a bioengineered Synechococcus sp. PCC 7002. The mutant strain was cultured in a photobioreactor to assess biomass yield, recombinant laminarinase activity, and CO2 uptake. The maximum enzyme activity was observed at a pH of 8.0 and a temperature of 70°C. At a CO2 concentration of 5%, we obtained a maximum specific growth rate of 0.083 h–1, a biomass productivity of 0.42 g?L–1?d–1, a biomass concentration of 3.697 g?L–1, and a specific enzyme activity of the mutant strain of 4.325 U?mg–1 dry mass. All parameters decreased as CO2 concentration increased from 5% to 10% and further to 15% CO2, except enzyme activity, which increased from 5% to 10% CO2. However, the mutant culture still grew at 15% CO2 concentration, as reflected by the biomass productivity (0.26 g?L–1?d–1), biomass concentration (2.416 g?L–1), and specific enzyme activity (3.247 U?mg–1 dry mass).
Porous carbon material facilitates the reaction SO2 + O2 + H2O → H2SO4 in coal-burned flue gas for sulfur resources recovery at mild conditions. It draws a long-term mystery on its heterogeneous catalysis due to the complicated synergic effect between its microstructure and chemical components. To decouple the effects of geometric structure from chemical components, classical molecular dynamics method was used to investigate the static and dynamic characteristics of the reactants (H2O, SO2 and O2) in the confined space truncated by double-layer graphene (DLG). Strong adsorption of SO2 and O2 by the DLG was observed, which results in the filling of the solute molecules into the interior of the DLG and the depletion of H2O. This effect mainly results from the different affinity of the DLG to the species and can be tuned by the separation of the two graphene layers. Such dimension dependence of the static and dynamic properties like distribution profile, molecular cluster, hydrogen bond and diffusion coefficient were also studied. The conclusions drawn in this work could be helpful to the further understanding of the underlying reaction mechanism of desulfurization process in porous carbon materials and other applications of carbon-based catalysts.
A sampling campaign including summer, autumn and winter of 2014 and spring of 2015 was accomplished to obtain the characteristic of chemical components in PM2.5 at three sites of Kunming, a plateau city in South-west China. Nine kinds of water-soluble inorganic ions (WSI), organic and element carbon (OC and EC) in PM2.5 were analyzed by ion chromatography and thermal optical reflectance method, respectively. Results showed that the average concentrations of total WSI, OC and EC were 22.85±10.95 µg·m-3, 17.83±9.57 µg·m-3 and 5.11±4.29 µg·m-3, respectively. They totally accounted for 53.0% of PM2.5. Secondary organic and inorganic aerosols (SOA and SIA) were also assessed by the minimum ratio of OC/EC, nitrogen and sulfur oxidation ratios. The annual average concentrations of SOA and SIA totally accounted for 28.3% of the PM2.5 concentration. The low proportion suggested the primary emission was the main source of PM2.5 in Kunming. However, secondary pollution in the plateau city should also not be ignorable, due to the appropriate temperature and strong solar radiation, which can promote the atmospheric photochemical reactions.
Ambient PM2.5 samples were collected at four sites in Xiamen, including Gulangyu (GLY), Hongwen (HW), Huli (HL) and Jimei (JM) during January, April, July and October 2013. Local source samples were obtained from coal burning power plants, industries, motor vehicles, biomass burning, fugitive dust, and sea salt for the source apportionment studies. The highest value of PM2.5 mass concentration and species related to human activities (SO42–, NO3–, Pb, Ni, V, Cu, Cd, organic carbon (OC) and elemental carbon (EC)) were found in the ambient samples from HL, and the highest and lowest loadings of PM2.5 and its components occurred in winter and summer, respectively. The reconstructed mass balance indicated that ambient PM2.5 consisted of 24% OM (organic matter), 23% sulfate, 14% nitrate, 9% ammonium, 9% geological material, 6% sea salt, 5% EC and 10% others. For the source profiles, the dominant components were OC for coal burning, motor vehicle, biomass burning and sea salt; SO42– for industry; and crustal elements for fugitive dust. Source contributions were calculated using a chemical mass balance (CMB) model based on ambient PM2.5 concentrations and the source profiles. GLY was characterized by high contributions from secondary sulfate and cooking, while HL and JM were most strongly affected by motor vehicle emissions, and biomass burning and fugitive dust, respectively. The CMB results indicated that PM2.5 from Xiamen is composed of 27.4% secondary inorganic components, 20.8% motor vehicle emissions, 11.7% fugitive dust, 9.9% sea salt, 9.3% coal burning, 5.0% biomass burning, 3.1% industry and 6.8% others.
Heterogeneous Fenton-like reaction has been extensively investigated to eliminate refractory organic contaminants in wastewater, but it usually shows low catalytic performance due to difficulty in reduction from Fe(III) to Fe(II). In this study, enhanced catalytic efficiency was obtained by employing Cu-doped BiFeO3 as heterogeneous Fenton-like catalysts, which exhibited higher catalytic performance toward the activation of H2O2 for phenol degradation than un-doped BiFeO3. BiFe0.8Cu0.2O3 displayed the best performance, which yielded 91% removal of phenol (10 mg L–1) in 120 min. The pseudo first-order kinetic rate constant of phenol degradation in BiFe0.8Cu0.2O3 catalyzed heterogeneous Fenton-like reaction was 5 times higher than those of traditional heterogeneous Fenton-like catalysts, such as Fe3O4 and goethite. The phenol degradation efficiency could still reach 83% after 4 cycles, which implied the good stability of BiFe0.8Cu0.2O3. The high catalytic activity of BiFe0.8Cu0.2O3 was attributed to the fact that the doping Cu into BiFeO3 could promote the generation of Fe(II) in the catalyst and then facilitate the activation of H2O2 to degrade the organic pollutants.
Chromium oxide and manganese oxide promoted ZrO2-CeO2 catalysts were prepared by a homogeneous precipitation method for the selective catalytic reduction of NOx with NH3. A series of characterization including X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), Brunauer–Emmett–Teller (BET) surface area analysis, H2 temperatureprogrammed reduction (H2-TPR), and X-ray photoelectron spectroscopy (XPS) were used to evaluate the influence of the physicochemical properties on NH3-SCR activity. Cr-Zr-Ce and Mn-Zr-Ce catalysts are much more active than ZrO2-CeO2 binary oxide for the low temperature NH3-SCR, mainly because of the high specific surface area, more surface oxygen species, improved reducibility derived from synergistic effect among different elements. Mn-Zr-Ce catalyst exhibited high tolerance to SO2 and H2O. Cr-Zr-Ce mixed oxide exhibited>80% NOx conversion at a wide temperature window of 100°C–300°C. In situ DRIFT studies showed that the addition of Cr is beneficial to the formation of Bronsted acid sites and prevents the formation of stable nitrate species because of the presence of Cr6 +. The present mixed oxide can be a candidate for the low temperature abatement of NOx.
The photolysis frequency of NO2, j(NO2), is an important analytical parameter in the study of tropospheric chemistry. A chemical actinometer (CA) was built to measure the ambient j(NO2) based on a high precision NOx instrument with 1 min time resolution. Parallel measurements of the ambient j(NO2) by using the CA and a commercial spectroradiometer (SR) were conducted at a typical urban site (Peking University Urban Environmental Monitoring Station) in Beijing. In general, good agreement was achieved between the CA and SR data with a high linear correlation coefficient (R2 = 0.977) and a regression slope of 1.12. The regression offset was negligible compared to the measured signal level. The j(NO2) data were calculated using the tropospheric ultraviolet visible radiation (TUV) model, which was constrained to observe aerosol optical properties. The calculated j(NO2) was intermediate between the results obtained with CA and SR, demonstrating the consistency of all the parameters observed at this site. The good agreement between the CA and SR data, and the consistency with the TUV model results, demonstrate the good performance of the installed SR instrument. Since a drift of the SR sensitivity is expected by the manufacturer, we propose a regular check of the data acquired via SR against those obtained by CA for long-term delivery of a high quality series of j(NO2) data. Establishing such a time series will be invaluable for analyzing the long-term atmospheric oxidation capacity trends as well as O3 pollution for urban Beijing.
Titanium dioxide (TiO2) is a widely used photocatalyst that has been demonstrated for microorganism disinfection in drinking water. In this study, a new material with a novel structure, silver and copper loaded TiO2 nanowire membrane (Cu-Ag-TiO2) was prepared and evaluated for its efficiency to inactivate E. coli and bacteriophage MS2. Enhanced photo-activated bactericidal and virucidal activities were obtained by the Cu-Ag-TiO2 membrane than by the TiO2, Ag-TiO2 and Cu-TiO2 membranes under both dark and UV light illumination. The better performance was attributed to the synergies of enhanced membrane photoactivity by loading silver and copper on the membrane and the synergistic effect between the free silver and copper ions in water. At the end of a 30 min test of deadend filtration under 254 nm UV irradiation, the Cu-Ag-TiO2 membrane was able to obtain an E. coli removal of 7.68 log and bacteriophage MS2 removal of 4.02 log, which have met the US EPA standard. The free metal ions coming off the membrane have concentrations of less than 10 ppb in the water effluent, far below the US EPA maximum contaminant level for silver and copper ions in drinking water. Therefore, the photo-activated disinfection by the Cu-Ag-TiO2 membrane is a viable technique for meeting drinking water treatment standards of microbiological water purifiers.
Because the efficiency of biological nutrient removal is always limited by the deficient carbon source for the low carbon/nitrogen (C/N) ratio in real domestic sewage, the denitrifying phosphorus removal (DNPR) was developed as a simple and efficient method to remove nitrogen and phosphorous. In addition, this method has the advantage of saving aeration energy while reducing the sludge production. In this context, a pre-denitrification anaerobic/anoxic/post-aeration + nitrification sequence batch reactor (pre-A2NSBR) system, which could also reduce high ammonia effluent concentration in the traditional two-sludge DNPR process, is proposed in this work. The pre-A2NSBR process was mainly composed of a DNPR SBR and a nitrifying SBR, operating as alternating anaerobic/anoxic/post-aeration + nitrification sequence. Herein, the long-term performance of different nitrate recycling ratios (0–300%) and C/N ratios (2.5–8.8), carbon source type, and functional microbial community were studied. The results showed that the removal efficiency of total inorganic nitrogen (TIN, including NH4+-N, NO2– -N, and NO3– -N) gradually increased with the nitrate recycling ratios, and the system reached the highest DNPR efficiency of 94.45% at the nitrate recycling ratio of 300%. The optimum C/N ratio was around 3.9–7.3 with a nitrogen and phosphorus removal efficiency of 80.15% and 93.57%, respectively. The acetate was proved to be a high-quality carbon source for DNPR process. The results of fluorescence in situ hybridization (FISH) analysis indicated that nitrifiers and phosphorus accumulating organisms (PAOs) were accumulated with a proportion of 19.41% and 26.48%, respectively.
A series of Co-La catalysts were prepared using the wet impregnation method and the synthesis of catalysts were modified by controlling pH with the addition of ammonium hydroxide or oxalic solution. All the catalysts were systematically investigated for NO oxidation and SO2 resistance in a fixed bed reactor and were characterized by Brunanuer–Emmett–Teller (BET) method, Fourier Transform infrared spectroscopy (FTIR), X–ray diffraction (XRD), Thermogravimetric (TG) and Ion Chromatography (IC). Among the catalysts, the one synthesized at pH = 1 exhibited the maximum NO conversion of 43% at 180°C. The activity of the catalyst was significantly suppressed by the existence of SO2 (300 ppm) at 220°C. Deactivation may have been associated with the generation of cobalt sulfate, and the SO2 adsorption quantity of the catalyst might also have effected sulfur resistance. In the case of the compact selective catalytic reduction (SCR), the activity increased from 74% to 91% at the highest gas hourly space velocity (GHSV) of 300000 h–1 when the NO catalyst maintained the highest activity, in excess of 50% more than that of the standard SCR.
The purpose of this work is to study the co-cultivation of Chlorella sp. and wastewater wild algae under different cultivation conditions (i.e. CO2, light intensity, cultivation time, and inoculation ratio) for enhanced algal biomass and lipid productivity in wastewater medium using Response Surface Methodology (RSM). The results show that mixed cultures of Chlorella sp. and wastewater wild algae increase biomass and lipid yield. Additionally, findings indicate that CO2, light intensity and cultivation time significantly affect algal productivity. Furthermore, CO2 concentration and light intensity, and CO2 concentration and algal composition, have an interactive effect on biomass productivity. Under different cultivation conditions, the response of algal biomass, cell count, and lipid productivity ranges from 2.5 to 10.2 mg/mL, 1.1 × 106 to 8.2 × 108 cells/mL, and 1.1 × 1012 to 6.8 × 1012 total fluorescent units/mL, respectively. The optimum conditions for simultaneous biomass and lipid accumulation are 3.6% of CO2 (v/v), 160 µmol/m2/s of light intensity, 1.6/2.4 of inoculation ratio (wastewater-algae/Chlorella), and 8.3 days of cultivation time. The optimal productivity is 9.8 (g/L) for dry biomass, 8.6 E + 08 (cells/mL) for cell count, and 6.8 E + 12 (Total FL units per mL) for lipid yield, achieving up to four times, eight times, and seven times higher productivity compared to nonoptimized conditions. Provided is a supportive methodology to improve mixed algal culture for bioenergy feedstock generation and to optimize cultivation conditions in complex wastewater environments. This work is an important step forward in the development of sustainable large-scale algae cultivation for cost-efficient generation of biofuel.
Extensive production and use of organophosphate pesticide in agriculture, has risen concerned about its ecotoxicity and risk assessment of insecticides, which are more important. Therefore, the present investigation was aimed to study the induction of oxidative stress and DNA damage by organophosphate insecticide profenofos (PFF) in freshwater snail Lymnea luteola (L. luteola). The median lethal value (96 h LC50) of PFF was estimated as 1.26 mg/L for L. luteola in a semi-static system and on the basis of LC50 value three concentrations viz., 0.126 (1/10 of LC50, Sublethal I), 0.63 (1/2 of LC50, Sublethal II) and 0.84 mg/L (2/3 of LC50, Sublethal III) were determined. Snails were exposed to above-mentioned concentrations of PFF along with solvent control (acetone) and negative control for 96 h. The haemolymph was collected at 24 and 96 h of after treatment. In heamolymph of PFF exposed snail, lipid peroxide, glutathione reduced glutathione S transferase and superoxide dismutase activities at the tested concentrations significantly differ from those in the control. The genotoxicity induced in hemocytes of treated snails was measured by alkaline single cell gel electrophoresis assay. The data of this experiment demonstrated significantly enhancement of oxidative stress and DNA damage in the treated snails as compared to controls. Also, we observed statistically significant correlations of ROS with DNA damage (% tail DNA) (R2 = 0.9708) for 24 h and DNA damage (R2 = 0.9665) for 96 h.
Results of the current experiment can be useful in risk evaluation of PFF among aquatic organisms. The study confirmed the use of comet assay for in vivo laboratory experiments using freshwater snail for selecting the toxic potential of industrial chemicals and environmental contaminants.
The spontaneous oxidation process of pristine silicon (Si) limits its application as photocatalyst or electrode in aqueous solution or moist air. Covering a protection layer on Si surface is an effective approach to overcome this disadvantage. In this paper, α-Fe2O3 is demonstrated to be an excellent alternative as a protection material. α-Fe2O3 layer was deposited around each p-type Si micropillar (SiMP) in well-ordered array by chemical bath deposition method. The diameter of SiMP was 5 mm and the thickness of α-Fe2O3 layer was about 20 nm. The photoeletrochemical stability of SiMP/α-Fe2O3 was proved by 10 circles cyclic voltammetry testing. Compared with SiMP, its optical absorption and photocurrent density improved 2 times and 4 times, respectively, and its onset potential for hydrogen evolution moved positively about 0.4 V. These improved performances could be ascribed to the enhanced photogenerated-charge-separation efficiency deriving from built-in electric field at the interface between Si and α-Fe2O3. The above results show an effective strategy to utilize Si material as photocatalyst or electrode in aqueous solution or moist air.
