Concurrent catalytic removal of typical volatile organic compound mixtures over Au-Pd/α-MnO2 nanotubes

α-MnO_2 nanotubes and their supported Au-Pd alloy nanocatalysts were prepared using hydrothermal and polyvinyl alcohol-protected reduction methods, respectively. Their catalytic activity for the oxidation of toluene/m-xylene, acetone/ethyl acetate, acetone/m-xylene and ethyl acetate/m-xylene mixtures was evaluated. It was found that the interaction between Au-Pd alloy nanoparticles and α-MnO_2 nanotubes significantly improved the reactivity of lattice oxygen, and the 0.91 wt.% Au0.48 Pd/α-MnO_2 nanotube catalyst outperformed the α-MnO_2 nanotube catalyst in the oxidation of toluene, m-xylene, ethyl acetate and acetone. Over the0.91 wt.% Au0.48 Pd/α-MnO_2 nanotube catalyst,(i) toluene oxidation was greatly inhibited in the toluene/m-xylene mixture, while m-xylene oxidation was not influenced;(ii) acetone and ethyl acetate oxidation suffered a minor impact in the acetone/ethyl acetate mixture; and(iii) m-xylene oxidation was enhanced whereas the oxidation of the oxygenated VOCs(volatile organic compounds) was suppressed in the acetone/m-xylene or ethyl acetate/m-xylene mixtures. The competitive adsorption of these typical VOCs on the catalyst surface induced an inhibitive effect on their oxidation, and increasing the temperature favored the oxidation of the VOCs. The mixed VOCs could be completely oxidized into CO_2 and H_2 O below 320°C at a space velocity of 40,000 m L/(g·hr). The 0.91 wt.% Au0.48 Pd/α-MnO_2 nanotube catalyst exhibited high catalytic stability as well as good tolerance to water vapor and CO_2 in the oxidation of the VOC mixtures. Thus, the α-MnO_2 nanotube-supported noble metal alloy catalysts hold promise for the efficient elimination of VOC mixtures.     

Simultaneous removal of ammonia and N-nitrosamine precursors from high ammonia water by zeolite and powdered activated carbon

When adding sufficient chlorine to achieve breakpoint chlorination to source water containing high concentration of ammonia during drinking water treatment, high concentrations of disinfection by-products(DBPs) may form. If N-nitrosamine precursors are present, highly toxic N-nitrosamines, primarily N-nitrosodimethylamine(NDMA), may also form. Removing their precursors before disinfection should be a more effective way to minimize these DBPs formation. In this study, zeolites and activated carbon were examined for ammonia and N-nitrosamine precursor removal when incorporated into drinking water treatment processes.The test results indicate that Mordenite zeolite can remove ammonia and five of seven N-nitrosamine precursors efficiently by single step adsorption test. The practical applicability was evaluated by simulation of typical drinking water treatment processes using six-gang stirring system. The Mordenite zeolite was applied at the steps of lime softening, alum coagulation, and alum coagulation with powdered activated carbon(PAC) sorption. While the lime softening process resulted in poor zeolite performance, alum coagulation did not impact ammonia and N-nitrosamine precursor removal. During alum coagulation, more than67% ammonia and 70%–100% N-nitrosamine precursors were removed by Mordenite zeolite(except 3-(dimethylaminomethyl)indole(DMAI) and 4-dimethylaminoantipyrine(DMAP)). PAC effectively removed DMAI and DMAP when added during alum coagulation. A combination of the zeolite and PAC selected efficiently removed ammonia and all tested seven N-nitrosamine precursors(dimethylamine(DMA), ethylmethylamine(EMA), diethylamine(DEA), dipropylamine(DPA), trimethylamine(TMA), DMAP, and DMAI) during the alum coagulation process.     

紫外诱变选育高原环境絮凝菌及其絮凝条件优化

为获得耐低温且絮凝优异的絮凝菌,对一株分离得到的絮凝菌进行紫外诱变和5℃低温胁迫培养,并对诱变优势菌进行应用条件优化.结果表明:①原始菌为蜡状芽孢杆菌（Bacillus cereus）.②紫外诱变和低温胁迫培养得到的目标诱变菌FB-5对生活污水絮凝率达75.35%,具有良好的遗传稳定性.③单因素试验确定最佳絮凝条件,即絮凝菌投加量为0.90 mL/（50 mL）、pH为7.4、助凝剂加量为1.0 mL/（50 mL）、处理时间为15 min;筛选出影响诱变菌絮凝能力最显著的3个因素为絮凝菌投加量、pH和助凝剂加量;通过Box-Behnken响应面试验得到最佳净化的应用条件,即絮凝菌投加量为0.90 mL/（50 mL）、pH为7.38、助凝剂加量为1.04 mL/（50 mL）.④验证试验确定絮凝率达97.01%,BOD₅、COD_Cr、浊度和色度去除率均达到97%以上,出水水质满足GB 18918—2002《城镇污水处理厂污染物排放标准》一级A标准.研究显示,紫外诱变联合低温胁迫技术以及单因素与响应面结合优化絮凝条件可以大幅度提高原始菌株的絮凝能力,低温诱变菌FM-5能使高寒地区城市生活污水中悬浮固体大幅降低,同时去除水体中多种污染物.      

中国生态用地及生态系统服务价值变化研究

生态用地具有重要的生态系统服务功能,在维护生态平衡、保障国土生态安全、应对全球气候变化中具有特殊地位。论文在总结国内研究学者有关生态用地研究成果的基础上,从生态系统服务功能入手,界定了生态用地的概念,根据生态干扰度构建了生态用地分类体系,并将生态用地分类与土地利用分类进行衔接,对全国生态用地的生态系统服务价值进行了评估,分析其特征及规律。研究表明：1）广义的生态用地是指能发挥供给、调节、支持生态系统服务功能,以及对维持区域生态平衡和调节全球气候具有重要作用的土地类型;2）依据“生态干扰度”构建了生态用地分类体系,将生态用地分为3个一级地类、5个二级地类和31个三级地类;3）2012年全国生态用地的生态系统服务价值为280 483.80亿元,呈现“西高、中次、东低”空间格局。2009—2012年全国生态用地的生态系统服务价值整体呈下降趋势,变化幅度空间分布差异较大,呈现“中增、东西减”的格局特点;2009—2012年全国生态用地各项生态系统服务功能受到损失,呈下降趋势,生态系统稳定性不容乐观。     

1970—2013年西北干旱区空中水汽含量时空变化与降水量的关系

论文基于1970—2013年西北干旱区高空和地面气象资料,采用多种统计学方法,分析了西北干旱区空中水汽含量的时空变化特征及其与降水量的关系。结果表明：1）1970—2002年,西北干旱区空中水汽含量呈显著的增加趋势,速率为0.835 mm/10 a（P<0.01）,其中以夏季增速最高（1.709 mm/10 a,P<0.01）;而降水效率基本稳定,仅春、冬季节略增。在空间上,1970—2002年水汽含量变化速率大小依次为北疆>南疆>河西走廊,其中冬、春季节以北疆水汽增速最大,夏、秋季节以南疆水汽增速最高。2）2003—2013年,西北干旱区水汽含量呈不显著下降趋势（-2.061 mm/10 a）;而降水效率明显增加,速率为0.136%/10 a,这说明近年来空中水汽转化为降水的效率明显提升。同时,北疆降水效率增加幅度明显高于其他地区。3）西北干旱区各季节的降水效率与降水量均呈显著正相关性,而水汽含量与降水量的相关性则表现出明显的季节性差异：春季>夏季>秋季>冬季。另外,新疆降水变化与水汽含量和降水效率均呈显著正相关性,而河西走廊降水量与降水效率的关系更为密切。     

Long-term observations of tropospheric NO2, SO2 and HCHO by MAX-DOAS in Yangtze River Delta area, China

Yangtze River Delta(YRD) area is one of the important economic zones in China. However,this area faces increasing environmental problems. In this study, we use ground-based multi-axis differential optical absorption spectroscopy(MAX-DOAS) network in Eastern China to retrieve variations of NO_2, SO_2, and formaldehyde(HCHO) in the YRD area. Three cities of YRD(Hefei, Nanjing, and Shanghai) were selected for long-term observations. This paper presents technical performance and characteristics of instruments, their distribution in YRD, and results of vertical column densities(VCDs) and profiles of NO_2, SO_2, and HCHO.Average diurnal variations of tropospheric NO_2 and SO_2 in different seasons over the three stations yielded minimum values at noon or in the early afternoon, whereas tropospheric HCHO reached the maximum during midday hours. Slight reduction of the pollutants in weekends occurred in all the three sites. In general trace gas concentrations gradually reduced from Shanghai to Hefei. Tropospheric VCDs of NO_2, SO_2, and HCHO were compared with those from Ozone Monitoring Instrument(OMI) satellite observations, resulting in R~2 of 0.606, 0.5432, and 0.5566, respectively. According to analysis of regional transports of pollutants, pollution process happened in YRD under the north wind with the pollution dissipating in the southeast wind. The feature is significant in exploring transport of tropospheric trace gas pollution in YRD, and provides basis for satellite and model validation.     

Insights into the formation of secondary organic carbon in the summertime in urban Shanghai

To investigate formation mechanisms of secondary organic carbon(SOC) in Eastern China,measurements were conducted in an urban site in Shanghai in the summer of 2015. A period of high O_3 concentrations(daily peak 120 ppb) was observed, during which daily maximum SOC concentrations exceeding 9.0 μg/(C·m~3). Diurnal variations of SOC concentration and SOC/organic carbon(OC) ratio exhibited both daytime and nighttime peaks. The SOC concentrations correlated well with O_x(= O_3+ NO_2) and relative humidity in the daytime and nighttime, respectively, suggesting that secondary organic aerosol formation in Shanghai is driven by both photochemical production and aqueous phase reactions. Single particle mass spectrometry was used to examine the formation pathways of SOC. Along with the daytime increase of SOC, the number fraction of elemental carbon(EC) particles coated with OC quickly increased from 38.1% to 61.9% in the size range of 250–2000 nm, which was likely due to gas-to-particle partitioning of photochemically generated semi-volatile organic compounds onto EC particles. In the nighttime, particles rich in OC components were highly hygroscopic, and number fraction of these particles correlated well with relative humidity and SOC/OC nocturnal peaks. Meanwhile, as an aqueous-phase SOC tracer, particles that contained oxalate-Fe(III) complex also peaked at night. These observations suggested that aqueous-phase processes had an important contribution to the SOC nighttime formation. The influence of aerosol acidity on SOC formation was studied by both bulk and single particle level measurements, suggesting that the aqueous-phase formation of SOC was enhanced by particle acidity.     

A comparison of chemical MSW compositional data between China and Denmark

Chemical waste compositions are important for municipal solid waste management, as they determine the pollution potentials from different waste strategies. A representative dataset for chemical characteristics of individual waste fractions is frequently required to assess chemical waste composition, but it is usually reported in developed countries and not in developing countries. In this study, a dataset for Chinese waste was established through careful data screening and assessment, named as CN dataset. Meanwhile, a dataset for Danish waste (DK dataset) was also summarized based on previous studies. In order to quantitatively evaluate the reliabilities of CN and DK datasets, the chemical waste compositions in four Chinese cities were estimated by utilizing both of them, respectively. It is indicated that the usage of CN datasets led to significantly lower discrepancies from the actual values based on laboratory analysis in most cases. Within the datasets, the moisture contents of food waste, paper, textiles, and plastics, the carbon content of food waste, as well as the oxygen content of plastics would induce significant divergences, which should be paid special attention when gathering the information. In addition, the fractional waste compositions in China showed similar features with other developing countries but differ significantly with developed countries. Thus the above-mentioned conclusions could also be true in other developing countries.     

Performance and mechanism of Cr(VI) removal by zero-valent iron loaded onto expanded graphite

Zero-valent iron (ZVI) was loaded on expanded graphite (EG) to produce a composite material (EG-ZVI) for efficient removal of hexavalent chromium (Cr(VI)). EG and EG-ZVI were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy and Brunauer–Emmett–Teller (BET) analysis. EG-ZVI had a high specific surface area and contained sub-micron sized particles of zero-valent iron. Batch experiments were employed to evaluate the Cr(VI) removal performance. The results showed that the Cr(VI) removal rate was 98.80% for EG-ZVI, which was higher than that for both EG (10.00%) and ZVI (29.80%). Furthermore, the removal rate of Cr(VI) by EG-ZVI showed little dependence on solution pH within a pH range of 1–9. Even at pH 11, a Cr(VI) removal rate of 62.44% was obtained after reaction for 1 hr. EG-ZVI could enhance the removal of Cr(VI) via chemical reduction and physical adsorption, respectively. X-ray photoelectron spectroscopy (XPS) was used to analyze the mechanisms of Cr(VI) removal, which indicated that the ZVI loaded on the surface was oxidized, and the removed Cr(VI) was immobilized via the formation of Cr(III) hydroxide and Cr(III)–Fe(III) hydroxide/oxyhydroxide on the surface of EG-ZVI.     

Behaviors and kinetics of toluene adsorption‐desorption on activated carbons with varying pore structure

This work was undertaken to investigate the behaviors and kinetics of toluene adsorption and desorption on activated carbons with varying pore structure. Five kinds of activated carbon from different raw materials were selected. Adsorption isotherms and breakthrough curves for toluene were measured. Langmuir and Freundlich equations were fitted to the equilibrium data, and the Freundlich equation was more suitable for simulating toluene adsorption. The process consisted of monolayer, multilayer and partial active site adsorption types. The effect of the pore structure of the activated carbons on toluene adsorption capacity was investigated. The quasi-first-order model was more suitable for describing the process than the quasi-second-order model. The adsorption data was also modeled by the internal particle diffusion model and it was found that the adsorption process could be divided into three stages. In the external surface adsorption process, the rate depended on the specific surface area. During the particle diffusion stage, pore structure and volume were the main factors affecting adsorption rate. In the final equilibrium stage, the rate was determined by the ratio of meso-and macro-pores to total pore volume. The rate over the whole adsorption process was dominated by the toluene concentration. The desorption behavior of toluene on activated carbons was investigated,and the process was divided into heat and mass transfer parts corresponding to emission and diffusion mechanisms, respectively. Physical adsorption played the main role during the adsorption process.