Effects of calcination temperature on physicochemical property and activity of CuSO4/TiO2 ammonia-selective catalytic reduction catalysts

CuSO_4/TiO_2 catalysts with high catalytic activity and excellent resistant to SO_2 and H_2 O,were thought to be promising catalysts used in Selective catalytic reduction of nitrogen oxides by NH_3.The performance of catalysts is largely affected by calcination temperature.Here,effects of calcination temperature on physicochemical property and catalytic activity of CuSO_4/TiO_2 catalysts were investigated in depth.Catalyst samples calcined at different temperatures were prepared first and then physicochemical properties of the catalyst were characterized by N2 adsorption-desorption,X-ray diffraction,thermogravimetric analysis,Raman spectra,Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,temperature-pro grammed desorption of NH_3,temperature-programmed reduction of H_2 and in situ diffuse reflectance infrared Fourier transform spectroscopy.Results revealed that high calcination temperature had three main effects on the catalyst.First,sintering and anatase transform into rutile with increase of calcination temperature,causing a decrement of specific surface area.Second,decomposition of CuSO_4 under higher calcination temperature,resulting in disappears of Br(?)nsted acid sites(S-OH),which had an adverse effect on surface acidity.Third,CuO from the decomposition of CuSO_4 changed surface reducibility of the catalyst and favored the process of NH_3 oxidation to nitrogen oxides(NO_x).Thus,catalytic activity of the catalyst calcined under high temperatures(≥600℃) decreased largely.     

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine

In this work, a series of Cu-ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N₂, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N₂ selectivity was impacted by the Brønsted acidity and the isolated Cu²⁺ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

Will polycentric cities cause more CO2 emissions? A case study of 232 Chinese cities

From 2000 to 2010 China experienced rapid economic development and urbanization. Many cities in economically developed areas have developed from a single-center status to polycentricity. In this study, we used exploratory spatial data analysis (ESDA) to identify the population centers, which identified 232 cities in China as having urban centers. COMP was used to represent urban agglomeration, and POLYD (representing how far is the city's sub-centers to the main center), POLYC (representing the number of a city's centers), and POLYP (representing the population distributed between the main center and the sub-centers) were used to indicate urban polycentricity. Night light data were used to determine the CO₂ emissions from various cities in China. A mixed model was used to study the impact of urban aggregation and polycentric data on the CO₂ emission efficiency in 2000 and 2010. The study found that cities with higher compactness were distributed in coastal areas, and the cities with higher multicentricity were distributed in the Yangtze River Delta and Shandong Province. The more compact the city was, the less conducive it was to improving CO₂ emission efficiency. Polycentric development of the city was conducive to improving the CO₂ emission efficiency, but the number of urban centers had no significant relationship with the CO₂ emission efficiency. Our research showed that the compactness and multicentricity of the city had an impact on the CO₂ emission efficiency and provided some planning suggestions for the low carbon development of the city.     

不同浓度锌处理下水稻幼苗对镉的累积效应

为探究锌（Zn）对水稻镉（Cd）累积的影响及其根表铁膜所发挥的作用,选取Cd高累积型水稻品种中9优547（简称"Z547"）和Cd低累积型水稻品种金优402（简称"J402"）,采用温室水培试验,研究0、2、5、10、15和20 μmol/L等6个Zn浓度下水稻幼苗对Cd的累积效应,以及不同浓度Zn处理对根表铁膜生成量的影响.结果表明:①随着c（Zn）的增加,Z547和J402水稻幼苗生物量均呈先增后减的趋势,分别在c（Zn）为2和10 μmol/L时达到最大值.②Z547和J402水稻幼苗中w（Cd）均呈先降后增的趋势,分别在c（Zn）为5和2 μmol/L时达到最小值;当水稻幼苗中w（Cd）达到最小值时,Z547根和地上部中w（Cd）分别为31.65和11.47 mg/kg,J402根和地上部中w（Cd）分别为22.58和14.36 mg/kg.③不同浓度Zn处理下水稻幼苗各部位中w（Cd）均与根表铁膜中w（Mn）、w（Fe）、w（Fe+Mn）呈显著正相关,高铁膜处理水稻幼苗中w（Cd）显著高于低铁膜处理,表明根表铁膜生成量的增加会促进Cd在水稻幼苗中的累积.研究显示,当c（Zn）较低时,c（Zn）的增加会抑制水稻幼苗对Cd的累积;当c（Zn）较高时,c（Zn）的增加会促进水稻幼苗对Cd的累积,而Zn可通过控制根表铁膜的生成来影响水稻幼苗对Cd的累积.      

On-going nitrification in chloraminated drinking water distribution system (DWDS) is conditioned by hydraulics and disinfection strategies

Within the drinking water distribution system (DWDS) using chloramine as disinfectant, nitrification caused by nitrifying bacteria is increasingly becoming a concern as it poses a great challenge for maintaining water quality. To investigate efficient control strategies, operational conditions including hydraulic regimes and disinfectant scenarios were controlled within a flow cell experimental facility. Two test phases were conducted to investigate the effects on the extent of nitrification of three flow rates (Q = 2, 6, and 10 L/min) and four disinfection scenarios (total Cl₂=1 mg/L, Cl₂/NH₃-N=3:1; total Cl₂=1 mg/L, Cl₂/NH₃-N=5:1; total Cl₂=5 mg/L, Cl₂/NH₃-N=3:1; and total Cl₂=5 mg/L, Cl₂/NH₃-N=5:1). Physico-chemical parameters and nitrification indicators were monitored during the tests. The characteristics of biofilm extracellular polymetric substance (EPS) were evaluated after the experiment. The main results from the study indicate that nitrification is affected by hydraulic conditions and the process tends to be severe when the fluid flow transforms from laminar to turbulent (2300<Re<4000). Increasing disinfectant concentration and optimizing Cl₂/NH₃-N mass ratio were found to inhibit nitrification to some extend when the system was running at turbulent condition (Q = 10 L/min, Re = 5535). EPS extracted from biofilm that was established at the flow rate of 6 L/min had greater carbohydrate/protein ratio. Furthermore, several nitrification indicators were evaluated for their prediction efficiency and the results suggest that the change of nitrite, together with total organic carbon (TOC) and turbidity can indicate nitrification potential efficiently.     

Coupling mechanism of activated carbon mixed with dust for flue gas desulfurization and denitrification

To clarify the effect of coking dust, sintering dust and fly ash on the activity of activated carbon for various industrial flue gas desulfurization and denitrification, the coupling mechanism of the mixed activated carbon and dust was investigated to provide theoretical reference for the stable operation. The results show that coking dust had 34% desulfurization efficiency and 10% denitrification efficiency; correspondingly, sintering dust and fly ash had no obvious desulfurization and denitrification activities. For the mixture of activated carbon and dust, the coking dust reduced the desulfurization and denitrification efficiencies by blocking the pores of activated carbon, and its inhibiting effect on activated carbon was larger than its own desulfurization and denitrification activity. The sintering dust also reduced the desulfurization efficiency on the activated carbon while enhancing the denitrification efficiency. Fly ash blocked the pores of activated carbon and reduced its reaction activity. The reaction activity of coking dust mainly came from the surface functional groups, similar to that of activated carbon. The reaction activity of sintering dust mainly came from the oxidative property of Fe₂O₃, which oxidized NO to NO₂ and promoted the fast selectively catalytic reduction (SCR) of NO to form N₂. Sintering dust was activated by the joint action of activated carbon, and both had a coupling function. Sintering dust enhanced the adsorption and oxidation of NO, and activated carbon further promoted the reduction of NO_x by NH₃; thus, the denitrification efficiency increased by 5%-7% on the activated carbon.     

Photodegradation of Hexafluoropropylene Oxide Trimer Acid under UV Irradiation

As a novel alternative to traditional perfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), hexafluoroproplyene oxide trimer acid (HFPO-TA) has been detected worldwide in surface water. Moreover, recent researches have demonstrated that HFPO-TA has stronger bioaccumulation potential and higher hepatotoxicity than PFOA. To treat these contaminants e.g. PFOA and PFOS, some photochemical techniques by adding exogenous substances had been reported. However, there is still no report for the behavior of HFPO-TA itself under direct UV irradiation. The current study investigated the photo-transformation of HFPO-TA under UV irradiation in aqueous solution. After 72 hr photoreaction, 75% degradation ratio and 25% defluorination ratio were achieved under ambient condition. Reducing active species, i.e., hydrated electrons and active hydrogen atoms, generated from water splitting played dominant roles in degradation of HFPO-TA, which was confirmed by different effects of reaction atmospheres and quenching experiments. A possible degradation pathway was proposed based on the products identification and theoretical calculations. In general, HFPO-TA would be transformed into shorter-chain PFASs, including hexafluoropropylene oxide dimer acid (HFPO-DA), perfluoropropionic acid (PFA) and trifluoroacetate (TFA). This research provides basic information for HFPO-TA photodegradation process and is essential to develop novel remediation techniques for HFPO-TA and other alternatives with similar structures.     

Polycyclic aromatic hydrocarbons in benthos of the northern Bering Sea Shelf and Chukchi Sea Shelf

Eighteen polycyclic aromatic hydrocarbons (PAHs) were detected in benthos collected onboard the ‘Snow Dragon’ in the Northern Bering Sea Shelf and Chukchi Sea Shelf during the 6^th Chinese National Arctic Research Expedition (CHINARE 2014). Σ₁₈PAHs for all biota samples ranged from 34.2 to 128.1 ng/g dry weight (dw), with the highest concentration observed in fish muscle (Boreogadus saida) samples close to St. Lawrence Island. The PAH composition pattern was dominated by the presence of lighter 3 ring (57%) and 2 ring (28%) PAHs, indicating oil-related or petrogenic sources as important origins of PAH contamination. Concentrations of alkyl-PAHs (1-methylnaphthalene and 2-methylnaphthalene) were lower than their parent PAH (naphthalene) in all biological tissue, and their percentage also decreased significantly (p<0.05) compared with those in the corresponding sediment. There were no significant relationships between PAH concentrations and trophic levels, which is possibly due to the combined results of the complex benthic foodweb in the subarctic/Arctic shelf region, as well as a low assimilation/effective metabolism for PAHs. According to toxic potency evaluation results from TCDD toxic equivalents (TEQs) and BaP-equivalent (BaPE) values, whelk (Neptunea heros) and starfish (Ctenodiscus crispatus) are two macroinvertebrate species showing relatively higher dioxin-like toxicity and carcinogenic risk.     

Particulate matter exchange between atmosphere and roads surfaces in urban areas

The deposition and the re-suspension of particulate matter (PM) in urban areas are the key processes that contribute not only to stormwater pollution, but also to air pollution. However, investigation of the deposition and the re-suspension of PM is challenging because of the difficulties in distinguishing between the resuspended and the deposited PM. This study created two Bayesian Networks (BN) models to explore the deposition and the re-suspension of PM as well as the important influential factors. The outcomes of BN modelling revealed that deposition and re-suspension of PM10 occurred under both, high-traffic and low-traffic conditions, and the re-suspension of PM2.5 occurred under low-traffic conditions. The deposition of PM10 under low-volume traffic condition is 1.6 times higher than under high-volume traffic condition, which is attributed to the decrease in PM10 caused by relatively higher turbulence under high-volume traffic conditions. PM10 is more easily resuspended from road surfaces compared to PM2.5 as the particles which larger than the thickness of the laminar airflow over the road surface are more easily removed from road surfaces. The increase in wind speed contributes to the increase in PM build-up by transporting particulates from roadside areas to the road surfaces and the airborne PM2.5 and PM10 increases with the increase in relative humidity. The study outcomes provide a step improvement in the understanding of the transfer processes of PM2.5 and PM10 between atmosphere and urban road surfaces, which in turn will contribute to the effective design of mitigation measures for urban stormwater and air pollution.