Highly selective catalytic reduction of NOxby MnOx–CeO2–Al2O3 catalysts prepared by self-propagating high-temperature synthesis

We first present preparation of MnOx–CeO_2–Al_2O_3 catalysts with varying Mn contents through a self-propagating high-temperature synthesis(SHS) method, and studied the application of these catalysts to the selective catalytic reduction of NOxwith NH3(NH_3-SCR).Using the catalyst with 18 wt.% Mn(18 MnCe1Al2), 100% NO conversion was achieved at 200°C and a gas hourly space velocity of 15384 hr-1, and the high-efficiency SCR temperature window, where NO conversion is greater than 90%, was widened to a temperature range of 150–300°C. 18 MnCe1Al2 showed great resistance to SO_2(100 ppm)and H_2O(5%) at 200°C. The catalysts were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller(BET) analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, and H_2 temperature programmed reduction. The characterization results showed that the surface atomic concentration of Mn increased with increasing Mn content, which led to synergism between Mn and Ce and improved the activity in the SCR reaction. 18 MnCe1Al2 has an extensive pore structure,with a BET surface area of approximately 135.4 m~2/g, a pore volume of approximately 0.16 cm~3/g, and an average pore diameter of approximately 4.6 nm. The SCR reaction on 18 MnCe1Al2 mainly followed the Eley-Rideal mechanism. The performances of the MnOx–CeO_2–Al_2O_3 catalysts were good, and because of the simplicity of the preparation process,the SHS method is applicable to their industrial-scale manufacture.     

Influence of metal ions on sulfonamide antibiotics biochemical behavior in fiber coexisting system

Metal ions and fiber are common compounds in the livestock and poultry manure,which will affect the fate of organic compounds in aqueous environment. However,limited research has addressed the effect of coexisting metal ions and fiber on the biodegradation of sulfonamide antibiotics. Accordingly, a compositing study was performed to assess the effect of metal ions(Fe3+and Cu2+) on the biodegradation of sulfadimethoxine sodium salt(SDM) in the presence of fiber. The enhanced adsorption of SDM onto fiber in the presence of metal ions can be attributed to the π+–π electron donor acceptor(EDA) interaction. The microbial(Phanerochaete chrysosprium) could easily attach onto fiber forming attached microbial, and the degradation rates of SDM of immobilized bacteria in the presence of Fe3 +were 100%, which were significantly higher than those of free bacteria(45%). This study indicates that Fe3 +and fiber could enhance the biodegradation of SDM. Fiber acts as adsorbent, carrier, and substrate which enhanced the removal of SDM.     

低温高铁锰氨氮地下水生物同池净化

为实现低温(5~6℃)高铁锰氨氮[TFe 9.0~12.0 mg·L~(-1)、Fe(Ⅱ)6.5~8.0 mg·L~(-1),Mn(Ⅱ)1.9~2.1 mg·L~(-1),NH_4~+-N 1.4~1.7 mg·L~(-1)]地下水生物同池净化,以中试模拟滤柱在某水厂进行了实验研究.结果表明,出水总铁在启动之初即能合格,出水氨氮和锰分别在72 d和75 d实现净化.工艺启动周期受培养温度和原水水质影响较大.滤速越大,锰的极限去除量越低,滤速≥1.0 m·h~(-1)时,锰的极限去除量为3.0 mg·L~(-1).锰是滤速提升的限制因素,工艺极限滤速是4.5m·h~(-1).滤速≤6.0 m·h~(-1)时,氨氮的极限去除量为1.5 mg·L~(-1),且不受滤速影响,溶解氧(dissolved oxygen,DO)不足导致工艺对更高浓度氨氮净化失败.DO充足的条件下,工艺净化所需滤层厚度随锰和氨氮浓度增加而增厚.滤速增大会导致铁锰氨氧化去除区间向滤层深处位移,发生"锰"溶出现象.进一步分析表明,铁和氨氮在滤层内可同步氧化去除;锰的高效氧化去除区间与铁和氨氮的高效氧化去除区间存在明显分级.     

基于液相31P核磁共振技术的人工河流沉积物中生物质磷形态特征的研究

利用液相~(31)P核磁共振技术分析了我国北部海河流域典型人工河流滏阳新河沉积物磷形态.结果发现,滏阳新河沉积物中共检测出6类磷化合物:正磷酸盐(Ortho-P)、磷酸单酯(Mono-P)、磷酯(Lipids-P)、DNA磷(DNA-P)、焦磷酸盐(Pyro-P)、膦酸盐(Phon-P).滏阳新河沉积物中的生物质磷包括膦酸盐(Phon-P,0.11%~1.57%)、磷酸单酯(Mono-P,8.96%~29.58%)、磷酯(Lipids-P,0.28%~2.66%)、DNA磷(DNA-P,0.75%~2.03%)、焦磷酸盐(Pyro-P,0.22%~0.86%),其中,磷酸单酯是生物质磷的主要组成部分.沿艾辛庄闸坝水流方向,磷化合物含量差异明显:闸坝附近TP和生物质磷含量最高,分别为6804.1 mg·kg~(-1)和1709.58 mg·kg~(-1);沿河流流向,TP变化率分别为84.97%、-24.11%、32.84%和-0.11%,生物质磷变化率分别为93.15%、-58.83%、42.65%和18.99%.上覆水中TP和SRP的平均浓度分别为3.0 mg·L~(-1)和2.6 mg·L~(-1),分别超过我国地表水环境质量标准(GB3838-2002)V类水标准(0.4 mg·L~(-1))7.5倍和6.5倍.基于液相~(31)P核磁共振技术,对人工河流水体磷的分布与传输有了全新的认知.因此,本研究可为深入认识磷在典型人工河流沉积物-水体系中的转化提供支持,有助于深入研究典型人工河流磷生物地球化学循环过程,同时为多闸坝人工河流的水流量调度与水生态构建提供数据支持.     

Optimising yield and resource utilisation of summer maize under the conditions of increasing density and reducing nitrogen fertilization

The inefficient use of resources always poses risks of maize (Zea mays L.) yield reduction in China. We performed this research to monitor the effects of increasing plant density and reducing nitrogen (N) rate on radiation-use efficiency (RUE), N efficiency traits, grain yield (GY) and their inter-relationships. Besides, whether GY and resource-use efficiency can both be maximized was examined. Hence, a 2-year field experiment was conducted using a widely grown variety “Denghai 618” in Shandong, China. Treatments contained two different plant densities [67,500 (D₁) and 97,500 (D₂) plant ha^?1] and three N levels [0 (N_?2), 180 (N_?1), 360 (N_ck) kg ha^?1], set D₁N_ck as control. Significant increases in grain yield, biomass, RUE, above-ground N uptake (AGN) and N efficiency were observed when density increased from D₁ to D₂. Declining N application was accompanied by reductions in yield, RUE and AGN especially under high density, yet an obvious improvement in N recovery efficiency (NRE), agronomic N efficiency and N partial factor productivity. The increased GY was positive related with population biomass (r = 0.895**), RUE (r = 0.769**) and AGN (r = 0.923**), whereas it has no significant correlation with N efficiency. In this study, D₂N_ck obtained 18.8, 17.9, 24.8 and 29.7% higher grain yield, RUE, AGN and NRE respectively, compared to control, optimizing both yield and the efficiencies of radiation and N use. Furthermore, higher yield and RUE with more desirable N efficiency may be possible via optimizing density and N rate combination.     

Evaluation of bacterial pathogen diversity, abundance and health risks in urban recreational water by amplicon next-generation sequencing and quantitative PCR

The microbial quality of urban recreational water is of great concern to public health.The monitoring of indicator organisms and several pathogens alone is not sufficient to accurately and comprehensively identify microbial risks.To assess the levels of bacterial pathogens and health risks in urban recreational water,we analyzed pathogen diversity and quantified four pathogens in 46 water samples collected from waterbodies in Beijing Olympic Forest Park in one year.The pathogen diversity revealed by 16 S r RNA gene targeted next-generation sequencing(NGS) showed that 16 of 40 genera and 13 of 76 reference species were present.The most abundant species were Acinetobacter johnsonii,Mycobacterium avium and Aeromonas spp.Quantitative polymerase chain reaction(q PCR) of Escherichia coli(uid A),Aeromonas(aer A),M.avium(16S r RNA),Pseudomonas aeruginosa(oaa) and Salmonella(inv A) showed that the aer A genes were the most abundant,occurring in all samples with concentrations of 10~(4–6) genome copies/100 m L,followed by oaa,inv A and M.avium.In total,34.8% of the samples harbored all genes,indicating the prevalence of these pathogens in this recreational waterbody.Based on the q PCR results,a quantitative microbial risk assessment(QMRA) showed that the annual infection risks of Salmonella,M.avium and P.aeruginosa in five activities were mostly greater than the U.S.EPA risk limit for recreational contacts,and children playing with water may be exposed to the greatest infection risk.Our findings provide a comprehensive understanding of bacterial pathogen diversity and pathogen abundance in urban recreational water by applying both NGS and q PCR.     

Template-free synthesis of inorganic hollow spheres at water/“water-brother”interfaces as Fenton-like reagents for water treatment

This paper reports a template-free method to synthesize a series of inorganic hollow spheres (IHSs) including Cu-1, Cu-2, Ni-1, Ni-2 based on mineralization reactions at water/“water-brother” interfaces. “Water-brother” was defined as a solvent which is miscible with water, such as ethanol and acetone. The water/“water-brother” interfaces are very different from water/oil interfaces. The “water-brother” solvent will usually form a homogenous phase with water. Interestingly, in our method, these interfaces can be formed, observed and utilized to synthesize hollow spheres. Utilizing the unique porous properties of the spheres, their potential application in water treatment was demonstrated by using Cu-1 IHSs as Fenton-like reagents for adsorption and decomposition of Congo Red from aqueous solution. The final adsorption equilibrium was achieved after 30 min with the maximum adsorption capacity of 86.1 mg/g, and 97.3% removal of the dye in 80 min after adsorption equilibrium. The IHSs can be reused as least 5 times after treatment by NaOH. This method is facile and suitable for large-scale production, and shows great potential for watertreatment.     

Transport and humification of dissolved organic matter within a semi-arid floodplain

In order to understand the transport and humification processes of dissolved organic matter(DOM) within sediments of a semi-arid floodplain at Rifle,Colorado,fluorescence excitation–emission matrix(EEM) spectroscopy,humification index(HIX) and specific UV absorbance(SUVA) at 254 nm were applied for characterizing depth and seasonal variations of DOM composition.Results revealed that late spring snowmelt leached relatively fresh DOM from plant residue and soil organic matter down into the deeper vadose zone(VZ).More humified DOM is preferentially adsorbed by upper VZ sediments,while non-or lesshumified DOM was transported into the deeper VZ.Interestingly,DOM at all depths undergoes rapid biological humification process evidenced by the products of microbial by-product-like(i.e.,tyrosine-like and tryptophan-like) matter in late spring and early summer,particularly in the deeper VZ,resulting in more humified DOM(e.g.,fulvic-acid-like and humic-acid-like substances) at the end of year.This indicates that DOM transport is dominated by spring snowmelt,and DOM humification is controlled by microbial degradation,with seasonal variations.It is expected that these relatively simple spectroscopic measurements(e.g.,EEM spectroscopy,HIX and SUVA) applied to depth-and temporally-distributed pore-water samples can provide useful insights into transport and humification of DOM in other subsurface environments as well.     

海南南渡江下游二维水动力及水生态数值模拟

为了模拟河流水生态系统演变,探讨热带河流浮游植物和浮游动物生物量在流量影响下的沿程变化规律,在求解河流二维浅水方程的基础上,考虑浮游动物、浮游植物、悬浮碎屑、无机氮、无机磷等输运和演变子模型以及各子模型间的耦合作用机制,构建水生态动力数学模型,并将该模型应用于我国热带河流—海南南渡江下游龙塘坝至入海口段（长约28 km）.数学模型采用ADI-QUICK格式差分方法对水动力学方程和对流扩散方程进行离散求解,进而驱动各类生物变量输运和演化.通过对河流水面线高程、营养盐含量、浮游生物生物量模拟值与实测值加以对比进行验证.实证结果表明,在生态参数合理率定前提下,忽略河流流量的时间变化,采用丰水期、平水期和枯水期工况下的代表流量加以概化,数值模拟仍能获得局部河段浮游生物生物量模拟值与实测值整体相符合的结果.浮游植物和浮游动物生物量均沿水流方向逐渐降低,但随流量的增大整体上呈降低趋势,丰水期上游浮游生物生物量为下游的1.6倍,枯水期达到9.3倍.受海水入侵、沿程污染排放等因素的影响,枯水期浮游生物生物量模拟值与实测值的偏差远大于丰水期.枯水期河道浮游植物和浮游动物生物量模拟值的最大值分别为77.71和38.56 mmol/m3（均以C计）,约为丰水期的3.8倍,说明枯水期水质富营养化风险远高于丰水期.      

Photodegradation of 17α-ethynylestradiol in dissolved humic substances solution: Kinetics, mechanism and estrogenicity variation

17α-Ethynylestradiol(EE2) in natural waters may cause adverse effects on organisms due to its high estrogenic potency. Laboratory studies were performed to study the effects of a local humic acid(LHA), fulvic acid(LFA) and Aldrich humic acid(AHA) on the photochemical behavior and estrogenic potency of EE2. Here photolytic experiments demonstrated that pure aqueous EE2 could undergo direct and self-sensitized photodegradation at a global rate of 0.0068 hr~(-1).Photodegradation rate of EE2 in 5.0 mg/L dissolved humic substances(DHS) was determined to be 0.0274, 0.0296 and 0.0254 hr~(-1) for LHA, LFA and AHA, respectively. Reactive oxygen species(ROS) and triplet dissolved humic substances(~3DHS*) scavenging experiments indicated that the promotion effect of DHS on EE2 photodegradation was mainly aroused by the reactions of HOU(35%–50%),~1O_2(10%) andDHS*(22%–34%). However, the photodegradation of EE2 could also be inhibited when DHS exceeded the threshold of 10 mg/L. Three hydroxylation products of EE2 were identified using GC–MS and their formation pathways were also proposed. In vitro estrogenicity tests showed that EE2 was transformed into chemicals without estrogenic potency. These findings could extend our knowledge on the photochemical behaviors of steroid estrogens in sunlit natural waters.