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.     

Responses of nitrification performance, triclosan resistome and diversity of microbes to continuous triclosan stress in activated sludge system

Triclosan(TCS) is commonly found in wastewater treatment plants,which often affects biological treatment processes.The responses of nitrification,antibiotic resistome and microbial community under different TCS concentrations in activated sludge system were evaluated in this study.The experiment was conducted in a sequencing batch reactor(SBR)for 240 days.Quantitative PCR results demonstrated that the abundance of ammonium oxidizing bacteria could be temporarily inhibited by 1 mg/L TCS and then gradually recovered.And the abundances of nitrite oxidizing bacteria(NOB) under 2.5 and 4 mg/L TCS were three orders of magnitude lower than that of seed sludge,which accounted for partial nitrification.When the addition of TCS was stopped,the abundance of NOB increased.The mass balance experiments of TCS demonstrated that the primary removal pathway of TCS changed from adsorption to biodegradation as TCS was continuously added into the SBR system.Moreover,TCS increased the abundance of mexB,indicating the efflux pump might be the main TCS-resistance mechanism.As a response to TCS,bacteria could secrete more protein(PN) than polysaccharide.Three-dimensional excitation-emission matrix revealed that tryptophan PN-like substances might be the main component in PN to resist TCS.High-throughput sequencing found that the relative abundances of Paracoccus,Pseudoxanthomonas and Thauera increased,which could secrete extracellular polymeric substances(EPS).And Sphingopyxis might be the main TCS-degrading bacteria.Overall,TCS could cause partial nitrification and increase the relative abundances of EPS-secreting bacteria and TCS-degrading bacteria.     

Ozone pollution characteristics and sensitivity analysis using an observation-based model in Nanjing, Yangtze River Delta Region of China

Ground-level ozone (O₃) has become a critical pollutant impeding air quality improvement in Yangtze River Delta region of China. In this study, we present O₃ pollution characteristics based on one-year online measurements during 2016 at an urban site in Nanjing, Jiangsu Province. Then, the sensitivity of O₃ to its precursors during 2 O₃ pollution episodes in August was analyzed using a box model based on observation (OBM). The relative incremental reactivity (RIR) of hydrocarbons was larger than other precursors, suggesting that hydrocarbons played the dominant role in O₃ formation. The RIR values for NO_X ranged from –0.41%/% to 0.19%/%. The O₃ sensitivity was also analyzed based on relationship of simulated O₃ production rates with reductions of VOC and NO_X derived from scenario analyses. Simulation results illustrate that O₃ formation was between VOCs-limited and transition regime. Xylenes and light alkenes were found to be key species in O₃ formation according to RIR values, and their sources were determined using the Positive Matrix Factorization (PMF) model. Paints and solvent use was the largest contributor to xylenes (54%), while petrochemical industry was the most important source to propene (82%). Discussions on VOCs and NO_X reduction schemes suggest that the 5% O₃ control goal can be achieved by reducing VOCs by 20%. To obtain 10% O₃ control goal, VOCs need to be reduced by 30% with VOCs/NO_X larger than 3:1.     

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.     

Metabolomic modulations in a freshwater microbial community exposed to the fungicide azoxystrobin

An effective broad-spectrum fungicide, azoxystrobin (AZ), has been widely detected in aquatic ecosystems, potentially affecting the growth of aquatic microorganisms. In the present study, the eukaryotic alga Monoraphidium sp. and the cyanobacterium Pseudanabaena sp. were exposed to AZ for 7 days. Our results showed that 0.2–0.5 mg/L concentrations of AZ slightly inhibited the growth of Monoraphidium sp. but stimulated Pseudanabaena sp. growth. Meanwhile, AZ treatment effectively increased the secretion of total organic carbon (TOC) in the culture media of the two species, and this phenomenon was also found in a freshwater microcosm experiment (containing the natural microbial community). We attempted to assess the effect of AZ on the function of aquatic microbial communities through metabolomic analysis and further explore the potential risks of this compound. The metabonomic profiles of the microcosm indicated that the most varied metabolites after AZ treatment were related to the citrate cycle (TCA), fatty acid biosynthesis and purine metabolism. We thereby inferred that the microbial community increased extracellular secretions by adjusting metabolic pathways, which might be a stress response to reduce AZ toxicity. Our results provide an important theoretical basis for further study of fungicide stress responses in aquatic microcosm microbial communities, as well as a good start for further explorations of AZ detoxification mechanisms, which will be valuable for the evaluation of AZ environmental risk.     

基于最大熵模型的福建省红树林潜在适生区评估

本研究利用生物气候、地形、底质类型、海温等环境因子和红树林分布数据建立了福建省红树林分布模型,基于最大熵方法分析了福建省沿岸红树林潜在适生区的空间分布.根据模型输出结果对福建省红树林的生境适宜性进行了评估,识别了影响红树林分布的关键环境因子及其适生值区间,并通过空间叠加分析获取了福建省红树林保护与修复的优先区与空缺区域.结果表明,影响福建省红树林适生区分布格局的主要环境因子包括海表温度、气温和降水等,福建省红树林潜在适生区主要位于沙埕港-三沙湾-兴化湾沿岸、泉州湾-厦门湾-九龙江口沿岸、漳江口-东山湾沿岸等地,其中最优适生区面积约为91km².全省共识别出8处红树林保护与修复的优先区域,现存红树林保护率约为64.4%,保护修复空缺主要出现在沙埕港、三沙湾、罗源湾、福清湾等处,研究结论可为未来福建省红树林保护和修复行动提供科学参考.     

滦河秋季大型底栖动物群落结构空间格局与关键环境影响因子识别

掌握水生生物的空间分布特征及其关键影响因子是科学制定生物多样性保护策略的基础.于2016年秋季对滦河53个样点开展了大型底栖动物和环境因子的现场调查,分析了大型底栖动物群落结构与空间分布特征,并识别出影响大型底栖动物物种空间分布的关键环境因子.结果表明:①滦河（河北省）共采集并鉴定出大型底栖动物206种,隶属于8纲22目70科144属,以纹石蚕（Hydropsyche sp.）和东方蜉蝣（Ephemera orientalis）为优势种.②根据滦河大型底栖动物群落结构相似性,53个样点在空间上被分为3组.第1组分布在滦河干流的中下游及支流下游,无指示物种;第2组分布在支流上游,指示种为纹石蚕、朝大蚊（Antocha sp.）和中华小长臂虾（Palaemonetes sinensis）;第3组分布在滦河干流中上游,指示种为东方蜉蝣和中华齿米虾（Neocaridina denticulate sinensis）.③第3组的分类单元数显著高于第1组和第2组;第1组的多样性指数显著高于第2组;第1组的均匀度指数显著高于其他2组.单因素方差分析（one-way ANOVA）发现,pH、TN、底质、河道变化、水质状况和河岸土地利用类型等环境因子在第2组与第3组之间差异显著,第2组明显高于第3组.典范对应分析（CCA）表明,栖境复杂性、河水水量状况和河岸土地利用类型是影响滦河大型底栖动物空间分布的关键环境因子.研究显示,降低河岸带干扰强度、恢复河道生境多样性是未来滦河大型底栖动物多样性保护恢复的重要管理措施.