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.
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.
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.
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.
Nutrients and water play an important role in microalgae cultivation. Using wastewater as a culture medium is a promising alternative to recycle nutrients and water, and for further developing microalgae-based products. In the present study, two species of microalgae, Chlorella sp. (high ammonia nitrogen tolerance) and Spirulina platensis (S. platensis, high growth rate), were cultured by using poultry wastewater through a two-stage cultivation system for algal biomass production. Ultrafiltration (UF) or centrifuge was used to harvest Chlorella sp. from the first cultivation stage and to recycle culture medium for S. platensis growth in the second cultivation stage. Results showed the two-stage cultivation system produced high microalgae biomass including 0.39 g·L–1Chlorella sp. and 3.45 g·L–1S. platensis in the first-stage and second-stage, respectively. In addition, the removal efficiencies of NH4+ reached 19% and almost 100% in the first and the second stage, respectively. Total phosphorus (TP) removal reached 17% and 83%, and total organic carbon (TOC) removal reached 55% and 72% in the first and the second stage, respectively. UF and centrifuge can recycle 96.8% and 100% water, respectively. This study provides a new method for the combined of pure microalgae cultivation and wastewater treatment with culture medium recycling.
In this study, a new water treatment system that couples (photo-) electrochemical catalysis (PEC or EC) in a microbial fuel cell (MFC) was configured using a stainless-steel (SS) cathode coated with Fe0/TiO2. We examined the destruction of methylene blue (MB) and tetracycline. Fe0/TiO2 was prepared using a chemical reduction-deposition method and coated onto an SS wire mesh (500 mesh) using a sol technique. The anode generates electricity using microbes (bio-anode). Connected via wire and ohmic resistance, the system requires a short reaction time and operates at a low cost by effectively removing 94% MB (initial concentration 20 mg?L–1) and 83% TOC/TOC0 under visible light illumination (50 W; 1.99 mW?cm–2 for 120 min, MFC-PEC). The removal was similar even without light irradiation (MFC-EC). The EEo of the MFC-PEC system was approximately 0.675 kWh?m–3?order–1, whereas that of the MFC-EC system was zero. The system was able to remove 70% COD in tetracycline solution (initial tetracycline concentration 100 mg?L–1) after 120 min of visible light illumination; without light, the removal was 15% lower. The destruction of MB and tetracycline in both traditional photocatalysis and photoelectrocatalysis systems was notably low. The electron spinresonance spectroscopy (ESR) study demonstrated that ?OH was formed under visible light, and ?O2– was formed without light. The bio-electricity-activated O2 and ROS (reactive oxidizing species) generation by Fe0/TiO2 effectively degraded the pollutants. This cathodic degradation improved the electricity generation by accepting and consuming more electrons from the bio-anode.
Investigation of demulsification of polybutadiene latex (PBL) wastewater by polyaluminum chloride (PAC) indicated that there was an appropriate dosage range for latex removal. The demulsification mechanism of PAC was adsorption-charge neutralization and its appropriate dosage range was controlled by zeta potential. When the zeta potential of the mixture was between -15 and 15 mV after adding PAC, the demulsification effect was good. Decreasing the latex concentration in chemical oxygen demand (COD) from 8.0 g/L to 0.2 g/L made the appropriate PAC dosage range narrower and caused the maximum latex removal efficiency to decrease from 95% to 37%. Therefore, more accurate PAC dosage control is required. Moreover, adding 50 mg/L sulfate broadened the appropriate PAC dosage range, resulting in an increase in maximum latex removal efficiency from 37% to 91% for wastewater of 0.2 g COD/L. The addition of sulfate will favor more flexible PAC dosage control in demulsification of PBL wastewater.
Conventional biological removal of nitrogen and phosphorus is usually limited due to the lack of biodegradable carbon source, therefore, new methods are needed. In this study, a new alternative consisting of enhanced biological phosphorus removal (EBPR) followed by partial nitritationanammox (PN/A), is proposed to enhance nutrients removal from municipal wastewater. Research was carried out in a laboratory-scale system of combined two sequencing batch reactors (SBRs). In SBR1, phosphorus removal was achieved under an alternating anaerobic-aerobic condition and ammonium concentration stayed the same since nitrifiers were washed out from the reactor under short sludge retention time of 2–3 d. The remaining ammonium was further treated in SBR2 where PN/A was established by inoculation. A maximum of nitrogen removal rate of 0.12 kg N?m–3?d–1 was finally achieved. During the stable period, effluent concentrations of total phosphorus and total nitrogen were 0.25 and 10.8 mg?L–1, respectively. This study suggests EBPR-PN/A process is feasible to enhance nutrients removal from municipal wastewater of low influent 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.
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.
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.
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.
In the present study, a novel approach was used to control zero valent iron aggregation and separation problems by fixing zero valent iron (ZVI) on bentonite-fly ash pellets. For this purpose, porous low cost bentonite-fly ash (BFA) pellets with size of 2.00 cm in length and 0.35 cm in diameter were prepared and fixed with ZVI to manufacture zero valent iron bentonite-fly ash (ZVI-BFA) pellets. Importantly, unlike powdered adsorbents, ZVI-BFA can easily be separated from final effluents when exhausted without any disintegration. The performance of the developed novel adsorbent was investigated for the removal of Pb2+ and Cd2+ from aqueous media. At 100 mg·L–1 and 1 g adsorbent, a maximum of 89.5% of Cd2+ and 95.6% of Pb2+ was removed by ZVI-BFA as compared to 56% and 95% removal by BFA. At 200 mg·L–1, Cd2+ and Pb2+ removal by ZVI-BFA was 56% and 99.8% respectively as compared to only 28% and 96% by BFA. Further, the removal kinetics was best fitted for pseudo-second order model. The study provides the basis for improving the removal capacity of porous materials by iron fixation while taking separation ability into consideration.
Mercury enrichment in response to elevated atmospheric mercury concentrations in the organs of rape (Brassica napus) was investigated using an open top chamber fumigation experiment and a soil mercury enriched cultivation experiment. Results indicate that the mercury concentration in leaves and stems showed a significant variation under different concentrations of mercury in atmospheric and soil experiments while the concentration of mercury in roots, seeds and seed coats showed no significant variation under different atmospheric mercury concentrations. Using the function relation established by the experiment, results for atmospheric mercury sources in rape field biomass showed that atmospheric sources accounted for at least 81.81%of mercury in rape leaves and 32.29% of mercury in the stems. Therefore, mercury in the aboveground biomass predominantly derives from the absorption of atmospheric mercury.
Sulfamethoxzole (SMX) and trimethoprim (TMP), two combined-using sulfonamide antibiotics, have gained increasing attention in the surface water, groundwater and the drinking water because of the ecological risk. The removal of TMP and SMX by artificial composite soil treatment system (ACST) with different infiltration rates was systematically investigated using K+, Na+, Ca2+, Mg2+ hydrogeochemical indexes. Batch experiments showed that the sorption onto the low-cost and commercially available clay ceramsites was effective for the removal of SMX and TMP from water. The column with more silty clay at high infiltration rate (1.394 m·d–1) had removal rates of 80% to 90% for TMP and 60% to 70% for SMX. High SMX and TMP removal rates had a higher effluent concentration of K+, Ca2+ and Mg2+ and had a lower effluent Na+ concentration. Removal was strongly related to sorption. The results showed that the removal of SMX and TMP was related to hydrogeochemical processes. In this study, ACST is determined to be applicable to the drinking water plants.
Nitrogen (N) and phosphorus (P) released from the sediment to the surface water is a major source of water quality impairment. Therefore, inhibiting sediment nutrient release seems necessary. In this study, red soil (RS) was employed to control the nutrients released from a black-odorous river sediment under flow conditions. The N and P that were released were effectively controlled by RS capping. Continuous-flow incubations showed that the reduction efficiencies of total N (TN), ammonium (NH4+-N), total P (TP) and soluble reactive P (SRP) of the overlying water by RS capping were 77%, 63%, 77% and 92%, respectively, and nitrification and denitrification occurred concurrently in the RS system. An increase in the water velocity coincided with a decrease in the nutrient release rate as a result of intensive water aeration.
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.
Transport of engineered antibiotic resistance plasmids in porous media has been reported to potentially cause significant spreading of antibiotic resistance in the environment. In this work, transport of an indigenous resistance plasmid pK5 in porous media was investigated through packed column experiments. At identical ionic strengths in CaCl2 solutions, the breakthroughs of pK5 from soil columns were very close to those from quartz sand columns, indicating that transport of pK5 in quartz sand and soil was similar. A similarity in transport behavior was also found between pK5 and an engineered plasmid pBR322 that has approximately the same number of base pairs as pK5. The influence of surfactants, a major group of constituents in soil solutions, was examined using an engineered plasmid pcDNA3.1(+)/myc-His A. The impact of an anionic surfactant, sodium dodecyl sulfate (SDS), was negligible at concentrations up to 200 mg·L–1. Cetyltrimethyl ammonium bromide (CTAB), a cationic surfactant, was found to significantly enhance plasmid adsorption at high concentrations. However, at environmentally relevant concentrations (<1 mg·L–1), the effect of this surfactant was also minimal. The negligible impact of surfactants and the similarity between the transport of engineered and indigenous plasmids indicate that under environmentally relevant conditions, indigenous plasmids in soil also have the potential to transport over long distances and lead to the spreading of antibiotic resistance.
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.
This work presents an overall introduction to the Station for Observing Regional Processes of the Earth System–SORPES in Nanjing, East China, and gives an overview about main scientific findings in studies of air pollution-weather/climate interactions obtained since 2011. The main results summarized in this paper include overall characteristics of trace gases and aerosols, chemical transformation mechanisms for secondary pollutants like O3, HONO and secondary inorganic aerosols, and the air pollution–weather/climate interactions and feedbacks in mixed air pollution plumes from sources like fossil fuel combustion, biomass burning and dust storms. The future outlook of the development plan on instrumentation, networking and data-sharing for the SORPES station is also discussed.
