Control of diffuse P-pollutants by multiple buffer/detention structures by Yuqiao Reservoir, North China

A case study on the transport process of agricultural diffuse P-pollutants was conducted in an experimental watershed locating in the north bank of Yuqiao Reservoir during 2001 and 2002. It was found that diversified artificial and natural buffer/detention landscape structures distributing along the ephemeral stream channel in this watershed played an important role of pollutants removal on downstream water quality, especially they have control effect on the diffuse P-pollutants transport process. Surface flow velocity was reduced sharply after passing through theses tructures. During continuous runoff events, the removal rate of TSS, TP, TDP, DRP by the whole system were 66.7%, 60.7%, 48.4%, and 43.3%, respectively. During discontinuous runoff events, removal rate of pollutants by the whole system was higher due to there was no or little surface water and pollutants exported from the watershed, of which removal rate of pollutants all exceeded 99%. The statistical analysis results of runoff events( n=8) indicated that dry pond was the steadiest structure for controlling diffuse P-pollutants export.     

Heterogeneous reaction of NO2 on the surface of montmorillonite particles

The studies on heterogeneous reactions over montmorillonite, which is a typical 2:1 layered aluminosilicate, will benefit to the understanding of heterogeneous reactions on clay minerals. Montmorillonite can be classified as sodium montmorillonite or calcium montmorillonite depending on the cation presented between the different layers. Using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), the heterogeneous reaction mechanism of NO₂ on the surface of montmorillonite was firstly investigated. Results showed that the reaction of NO₂ on the surface of sodium and calcium montmorillonite fit a first-order kinetics, and the reaction duration of calcium montmorillonite was longer than that of sodium montmorillonite under the dry condition. For either sodium or calcium montmorillonite, the uptake coefficient decreased as humidity increased.     

Two alternative modes for di use pollution control in Wuhan City Zoo

Pollution in urban zoos arises from diffuse and small point sources. However, its control has received little attention in past decades. Online and ofttine modes of ecological engineering technology were designed to control pollution from small point and diffuse sources in Wuhan City Zoo, China. Their characteristics and performances were investigated in sixteen runoff events from 2003 to 2005. The results showed that the two modes both improved runoff water quality and had high retention rates for water and pollutants. In the outflows, the event mean concentrations （EMCs） of total suspended solids （TSS）, chemical oxygen demand （COD）, total nitrogen （TN） and total phosphorus （TP） were reduced by 88%, 59%, 46% and 71% for the online mode, and those were 77%, 42%, 50% and 66% for the ofttine mode. The annual retention rates of pollutant loads for the online mode were 94.9%-98.5% in the three study years; those for the ofitine mode were 70.5%-86.4%. Based on calculation, the online mode was able to store the runoff of 66.7 mm rainfall completely, and the ofttine mode could store that of 31.3 mm rainfall. In addition, the online mode can provide an effective way for rainwater utilization and good habitats for aquatic wildlives, and has an excellent aesthetics value for recreationsal pastimes. The ofiline mode can save land resources and may be an effective and economical measure for diffuse pollution control in urban areas.     

Adsorption of Ca2+ on single layer graphene oxide

Graphene oxide(GO) holds great promise for a broad array of applications in many fields,but also poses serious potential risks to human health and the environment.In this study,the adsorptive properties of GO toward Ca~(2+) and Na+were investigated using batch adsorption experiments,zeta potential measurements,and spectroscopic analysis.When pH increased from 4 to 9,Ca~(2+)adsorption by GO and the zeta potential of GO increased significantly.Raman spectra suggest that Ca~(2+)was strongly adsorbed on the GO via –COO Ca~+ formation.On the other hand,Na+was adsorbed into the electrical diffuse layer as an inert counterion to increase the diffuse layer zeta potential.While the GO suspension became unstable with increasing pH from 4 to 10 in the presence of Ca~(2+),it was more stable at higher pH in the NaC l solution.The findings of this research provide insights in the adsorption of Ca~(2+)on GO and fundamental basis for prediction of its effect on the colloidal stability of GO in the environment.     

Synergistic effect of N- and F-codoping on the structure and photocatalytic performance of TiO2

Three types of TiO₂ nanostructures were synthesized via a facile hydrolysis method at 195 ℃. Effects of the preparation method and doping with N and F on the crystal structure and photocatalytic performance of TiO₂ were investigated. The nanomaterials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller porosimetry, ultraviolet-visible diffuse reflectance spectroscopy and fluorescent emission spectra. Their photo-catalytic activity was examined by the photodegradation of methylene blue in aqueous solution under both ultra-violet and visible light irradiation. The results show that nitrogen and fluorine co-doped anatase TiO₂ had the characteristics of a smaller crystalline size, broader light absorption spectrum and lower charge recombination than pure TiO₂. Most importantly, more efficient photocatalytic activity under both ultra-violet and visible light was observed. The obtained N-F-TiO₂ nanomaterial shows considerable potential for water treatment under sunlight irradiation.     

Photocatalytic degradation of paraquat using nano-sized Cu-TiO2/SBA-15 under UV and visible light

Photocatalytic degradation of paraquat using mesoporous-assembled Cu-TiO₂/SBA15 under UV and visible light was investigated. The catalyst was synthesized by impregnation of Cu-TiO₂ colloids onto SBA-15. The colloids of Cu-TiO₂ were prepared via sol-gel method while the mesoporous support was prepared using hydrothermal technique. The catalyst was characterized using X-ray diffraction, nitrogen adsorption-desorption, transmission electron microscopy, UV diffuse reflectance spectroscopy, Zeta potential and X-ray adsorption spectroscopy. Results from characterizations showed that Cu doped TiO₂ had a small crystalline size and was well-dispersed on SBA-15. The inclusion of SBA-15 significantly enhanced the photocatalytic activity of the catalyst. Among the three types of undoped catalyst in this study (P25, TiO₂, TiO₂/SBA-15), TiO₂/SBA-15 yielded the highest degradation of paraquat for all pH under UV illumination. Meanwhile 2 wt.% Cu-TiO₂/SBA-15 yielded the highest activity under visible light.     

Probing and understanding interaction of Eu(III) with γ- alumina in presenceof malonic acid

Radionuclide migration in aquatic environment is influenced by its sorption onto colloids/mineral oxides and the presence of organic complexing anions. With a view to understand the sorption of trivalent actinides by mineral oxides in presence of organic acid, in the present study, Eu(III), malonic acid (MA) and γ-alumina are considered as representatives of trivalent actinides, low molecular weight natural occurring organic acid and aluminol sites, respectively. The influence of MA on sorption of Eu(III) by γ-alumina was elucidated by batch sorption, spectroscopic techniques and surface complexation modeling, for the first time. Attenuated Total Reflection-Fourier Transform Infrared spectroscopic studies of MA sorbed on γ-alumina revealed the presence of two inner-sphere surface complexes. Batch sorption for binary (alumina-Eu(III)) and ternary (alumina-Eu(III)-MA) systems were investigated as a function of pH, Eu(III) concentration and sequential addition of Eu(III)/MA. The pH edge for Eu(III) sorption shifts to higher pH with increasing Eu(III) concentration. In ternary systems, Eu(III) sorption is significantly enhanced at pH < 4.5. Eu(III) speciation on γ-alumina is independent of addition sequence of Eu(III)/MA. Time resolved fluorescence spectroscopy of Eu(III) sorbed on γ-alumina exhibited two surface species, XOEu²⁺ and (YO)₂Eu⁺. The enhancement in I₆₁₆/I₅₉₂ and lifetime for ternary systems, as compared to binary system, at low pH, indicates the participation of Eu-MA complexes in the formation of surface species in ternary systems. The diffuse layer model has been employed to successfully model the experimental sorption profiles of binary and ternary systems, using code FITEQL 4.0, by considering the surface species identified by spectroscopic techniques.     

Metals in sediment/pore water in Chaohu Lake: Distribution, trends and flux

Nine metals, Cd, Cu, Ni, Pb, As, Cr, Zn, Fe, and Mn in sediment and pore water from 57 sampling sites in Chaohu Lake (Anhui Province, China) were analyzed for spatial distribution, temporal trends and diffuse flux in 2010. Metals in the surface sediment were generally the highest in the western lake center and Nanfei-Dianbu River estuary, with another higher area of As, Fe, and Mn occurring in the Qiyang River estuary. Metal contamination assessment using the New York sediment screening criteria showed that the sediment was severely contaminated in 44% of the area with Mn, 20% with Zn, 16% with Fe, 14% with As, and 6% with Cr and Ni. An increasing trend of toxic metals (Cd, Cu, Ni, Pb, As, Cr, Zn) and Mn with depth was shown in the western lake. Compared with metal content data from the sediment survey conducted in 1980s, the metal content of surface sediment in 2010 was 2.0 times that in the 1980s for Cr, Cu, Zn, and As in the western lake, and less than 1.5 times higher for most of the metals in the eastern lake. Among the metals, only Mn and As had a widespread positive diffuse flux from the pore water to overlying water across the whole lake. The estimated flux in the whole lake was on average 3.36 mg/(m². day) for Mn and 0.08 mg/(m². day) for As, which indicated a daily increase of 0.93 μg/L for Mn and 0.02 μg/L for As in surface water. The increasing concentration of metals in the sediment and the flux of metals from pore water to overlying water by diffusion and other physical processes should not be ignored for drinking-water sources.     

Catalytic combustion of soot over ceria-zinc mixed oxides catalysts supported onto cordierite

Modified substrates as outer heterogeneous catalysts was employed to reduce the soot generated from incomplete combustion of diesel or diesel/biodiesel blends, a process that harms the environment and public health. The unique storage properties of ceria(CeO2) makes it one of the most efficient catalysts available to date. Here, we proposed that ceria-based catalysts can lower the temperature at which soot combustion occurs; more specifically, from 610℃ to values included in the diesel exhausts operation range(300–450℃). The sol-gel method was used to synthesize mixed oxide-based catalysts(CeO2:ZnO); the resulting catalysts were deposited onto cordierite substrates. In addition, the morphological and structural properties of the material were evaluated by XRD, BET, TPR-H2, and SEM. Thermogravimetric(TG/DTA) analysis revealed that the presence of the catalyst decreased the soot combustion temperature by 200℃ on average, indicating that the oxygen species arise at low temperatures in this situation, promoting highly reactive oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy(DRS) showed that catalyst-impregnated cordierite samples efficiently oxidized soot in a diesel/biodiesel stationary motor: soot emission decreased by more than 70%.     

Insights into metals in individual fine particles from municipal solid waste using synchrotron radiation-based micro-analytical techniques

Excessive inter-contamination with heavy metals hampers the application of biological treatment products derived from mixed or mechanically-sorted municipal solid waste (MSW). In this study, we investigated fine particles of < 2 mm, which are small fractions in MSW but constitute a significant component of the total heavy metal content, using bulk detection techniques. A total of 17 individual fine particles were evaluated using synchrotron radiation-based micro-X-ray fluorescence and micro-X-ray diffraction. We also discussed the association, speciation and source apportionment of heavy metals. Metals were found to exist in a diffuse distribution with heterogeneous intensities and intense hot-spots of < 10 μm within the fine particles. Zn-Cu, Pb-Fe and Fe-Mn-Cr had significant correlations in terms of spatial distribution. The overlapped enrichment, spatial association, and the mineral phases of metals revealed the potential sources of fine particles from size-reduced waste fractions (such as scraps of organic wastes or ceramics) or from the importation of other particles. The diverse sources of heavy metal pollutants within the fine particles suggested that separate collection and treatment of the biodegradable waste fraction (such as food waste) is a preferable means of facilitating the beneficial utilization of the stabilized products.     

河谷型城市风场及污染物扩散的CFD数值仿真

为研究河谷型城市地形及其引起的风场和污染物扩散的复杂问题,利用CFD（计算流体力学）方法和复杂地形网格生成技术,建立河谷型城市风场及大气污染分布的数值仿真模型,实现CFD方法在复杂地形空气运动和污染物扩散方面的应用.分别使用LES（large eddy simulation）模型和mixture模型研究兰州市地面风场特征和污染物扩散形态,计算得到的污染物分布结果与实测结果分布一致.结果表明:复杂地形对空气运动的影响很大,如风速因山体屏障作用会呈现带状分布特征,山体后侧易出现弱风区域;同时,风场会密切影响污染物扩散,决定了污染物扩散形态,如幅散能够影响污染物扩散范围及污染水平.而给定西北风条件下,如地面以上10 m、风速为5 m/s、不受地形阻挡情况下,工业区污染物浓度被稀释10倍,约扩散2.2 km;山体阻挡会抑制污染物纵向扩散,表现在山体阻挡情况下污染物稀释100倍时的扩散长度约为相对平坦区域的1/3.此外,不同的入口风向会引起空气运动与山体相互作用发生变化,进而会使得地面风速、局部风场存在差异,造成污染物扩散及分布形态差异.研究显示,CFD方法可行,模型可靠,可以用来研究地形对风场和污染物扩散的影响.      

气旋活动对福岛核污染物扩散影响的模拟研究

基于拉格朗日粒子扩散模式FLEXPART-WRF,根据Stohl推导的日本福岛第一核电站核事故(下称福岛核事故)发生后40 d内的137Cs排放量数据,对核污染物在中尺度区域的扩散传输进行数值模拟研究,并选取近5年3次典型气旋个例(北方气旋、南方气旋和缓慢移动气旋)进行敏感性试验,以分析不同气旋系统对污染物扩散的影响. 结果表明:福岛核事故发生后,受中纬度西风带影响,核污染物主要向东部太平洋方向扩散;核事故发生后的5 d,受北方气旋和日本南部局地中尺度气旋2次气旋过程的影响,核污染物对日本本土部分地区影响较大,但影响时间不长. 典型气旋个例的敏感性模拟试验结果表明:北方气旋和南方气旋均可使核污染物对日本本土造成一定的影响,但由于气旋移动速度较快,影响日本岛的时间较短,沉降量也较小;当出现缓慢移动气旋影响日本和周边地区时,可致污染物影响日本岛的时间延长,并直接进入东亚大陆.      

Effect of TiO2 calcination temperature on the photocatalytic oxidation of gaseous NH3

Carbon-modified titanium dioxide(TiO2) was prepared by a sol-gel method using tetrabutyl titanate as precursor, with calcination at various temperatures, and tested for the photocatalytic oxidation(PCO) of gaseous NH3 under visible and UV light. The test results showed that no samples had visible light activity, while the TiO2 calcined at 400℃ had the best UV light activity among the series of catalysts, and was even much better than the commercial catalyst P25. The catalysts were then characterized by X-ray diffractometry, Brunauer-Emmett-Teller adsorption analysis, Raman spectroscopy, thermogravimetry/differential scanning calorimetry coupled with mass spectrometry, ultraviolet-visible diffuse reflectance spectra, photoluminescence spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy. It was shown that the carbon species residuals on the catalyst surfaces induced the visible light adsorption of the samples calcined in the low temperature range( 300℃). However, the surface acid sites played a determining role in the PCO of NH3 under visible and UV light over the series of catalysts. Although the samples calcined at low temperatures had very high SSA, good crystallinity, strong visible light absorption and also low PL emission intensity, they showed very low PCO activity due to their very low number of acid sites for NH3 adsorption and activation. The TiO2 sample calcined at 400℃ contained the highest number of acid sites among the series of catalysts, therefore showing the highest performance for the PCO of NH3 under UV light.     

海南岛地区大气输送和扩散特征的数值模拟

采用中尺度气象模式WRF及风场诊断模式CALMET,结合轨迹分析和拉格朗日随机游走模拟方法,分析了海南岛地区低层大气中尺度水平输送和扩散特性,并计算了各季平均大气扩散模态.结果表明,该区域大气污染物的扩散和输送主要受到大尺度背景环流、海陆风等局地环流及地形绕流等的影响.海陆风局地环流是沿海城市源排放的大气污染物向海南本岛输送和扩散的主要机制.北部城市海口的大气扩散对岛内影响最大,冬季平均影响范围可覆盖西北半部;春、秋季主要影响西北和北部区域;夏季对本岛的影响仅限于北部沿岸.南部城市三亚的大气扩散对岛内影响较小,秋季向西南海面的扩散对本岛几乎没有影响;冬、春季对三亚以西沿岸的影响有所增加;夏季扩散影响全面指向岛内,并因地形的作用而东、西向大角度扩展,影响海岛南部的大部分沿岸地区.西北部昌江的平均输送扩散方向与当地海岸线的走向基本一致,污染影响不易深入到岛内.其中,秋季扩散影响以偏西南方向为主,仅对昌江西南部分海岸有少量影响;冬、春季扩散形态类似但影响范围扩大到以东方市为代表的低山盆地地带;海岛西北部大部分沿海地带可受到昌江夏季扩散的影响,但平均扩散方向指向东北偏北的海面.     

Response surface methodology analysis of the photocatalytic removal of Methylene Blue using bismuth vanadate prepared via polyol route

Visible-light driven photocatalyst bismuth vanadate (BiVO₄) photocatalyst was synthesized by the polyol route using ethylene glycol. The precipitate was washed, dried and calcined at 450℃ for 3 hr. The sample was characterized by X-ray diffractometry (XRD), field emission scanning electron microscopy (FE-SEM), zeta potential, surface area (BET method) and band gap energy via diffuse reflectance spectroscopy (DRS). The synthesized BiVO₄ has a monoclinic phase with a surface area of 4.3 m²/g and a band gap energy of 2.46 eV. A majority of the particles were in the range of 90-130 nm as obtained from the particle size distribution histrogram. The efficiency of the sample as a visible-light driven photocatalyst was examined by photodegrading Methylene Blue (MB). The effects of some operational photodegradation parameters such as mass loading, initial dye concentration and pH were also examined. Experimental design methodology was applied by response surface modeling and optimization of the removal of MB. The multivariate experimental design was employed to develop a quadratic model as a functional relationship between the percentage removal of MB and three experimental factors (BiVO₄ loading, MB initial concentration and pH). The percentage removal of MB approached 67.21% under optimized conditions. In addition, a satisfactory goodness-of-fit was achieved between the predictive and the experimental results.     

长江三角洲冬季一次低能见度过程的地区差异和气象条件

采用NCEP再分析资料、MICAPS地面、高空气象资料以及国家环保部空气质量监测资料,对2014年2月20~22日长江三角洲地区一次低能见度过程地区差异和气象条件进行了分析.天气形势分析表明,长三角地面处在高压的控制下,地面风速较小,使污染物积累,有利于低能见度(雾-霾)的形成和维持.根据不同区域的雾、霾分布和日变化特征,将长江三角洲地区分为3个子区域:I区为江苏大部(雾霾混合型),II区为上海及其周边(霾类型),III区为浙江大部(雾类型),该区域白天能见度较高,夜间能见度较低的特征是由湿度因子造成的.影响I区能见度变化的主要原因是:热力原因:大气对流层低层的层结稳定;湿度原因为:空气较湿润,气溶胶粒子吸湿性增长;动力原因主要是垂直方向和水平方向的大气扩散能力弱;污染因子对能见度变化的影响较小.影响II区能见度变化的主要原因是PM2.5浓度高导致的污染,热力因子、湿度因子和动力因子对能见度的变化影响很小.影响III区能见度变化的热力原因是:大气对流层低层层结稳定、近地面存在逆温;湿度原因是因为:空气较湿润,气溶胶粒子吸湿性增长;动力原因是因为边界层高度较低导致的垂直扩散能力较差.各个区域的气象因子解释方差的计算结果表明:I区湿度因子和动力因子对能见度的影响更大,III区.湿度因子对能见度的影响更大.     

Acid-treated Fe-doped TiO2 as a high performance photocatalyst used for degradation of phenol under visible light irradiation

The photocatalytic activity of Fe-doped TiO2 nanoparticles is significantly increased by an acid-treatment process. The photocatalyst nanoparticles were prepared using sol–gel method with 0.5 mol% ratio of Fe:Ti in acidic pH of 3. The nanoparticles were structurally characterized by means of X-ray diffraction(XRD), high-resolution transmission electron microscope(HRTEM), energy-dispersive X-ray spectroscopy(EDX), X-ray photoelectron spectroscopy(XPS) and diffuse reflectance spectroscopy(DRS). It was observed that the photocatalytic activity suffered from an iron oxide contaminating layer deposited on the surface of the nanoparticles. This contamination layer was removed using an HCl acidtreatment process. The photocatalytic activity using 500 mg/L of Fe0.5-TiO2 in a 10 mg/L of phenol solution increased significantly from 33% to 57%(about 73% increase in the performance), within 90 min of reaction time under visible light irradiation. This significant improvement was achieved by removing the iron oxide contamination layer from the surface of the nanoparticles and adjusting p H to mild acidic and basic pHs.     

新疆天山北坡低层大气稀释扩散能力的季节性差异和量化研究

随着我国重点区域空气质量水平的整体改善,新疆天山北坡的污染问题日显突出. 为了探究当地低层大气稀释扩散能力的季节性差异及其对污染的影响,综合运用多种观测资料,对PM_2.5污染和气象条件的季节性差异及二者之间的联系进行了系统分析,并利用区域空气质量模型开展数值试验,对低层大气稀释扩散能力进行了量化. 结果表明:①天山北坡主要城市冬季(12月—翌年1月)和春夏季(5—8月)PM_2.5浓度最大可相差10.8倍. 对环流形势、地面气象要素、下垫面和低层大气层结等气象条件分析发现,低层大气稀释扩散能力是造成PM_2.5浓度差异较大的首要外因. ②天山北坡主要城市春夏季的低层大气稀释扩散能力远高于冬季,最高为冬季的4.9倍;稀释扩散能力的逐月变化表明,稀释扩散能力最强和最弱月份最大相差5.6倍. 而同处北方的京津冀地区,春夏季与冬季最大相差2.0倍. 研究显示,合理利用低层大气稀释扩散能力的季节性差异,施行系统性的错峰生产,竭力减少冬季大气污染物排放,将是改善天山北坡城市空气质量的有效途径.      

Laboratory simulation of SO_2 heterogeneous reactions on hematite surface under different SO_2 concentrations

The variations of sulfate formation and optical coefficients during SO2 heterogeneous reactions on hematite surface under different SO2 concentrations were examined using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatograph (IC). Laboratory experiments revealed that within ambient SO2 of 0.51–18.6 ppmv, sulfate product, producing velocity, absorption and backward scattering coefficients showed an increasing trend with SO2 concentration. Under given SO2 concentra...     

高架桥对街道峡谷内大气颗粒物输运的影响

随着我国城市汽车保有量的迅速攀升,城市中心区域的空气质量与生态环境急剧恶化.利用计算流体力学(CFD)数值模拟,研究了3种H/W(街道建筑物高度/峡谷宽度)下高架桥对街道峡谷内颗粒物扩散的影响.建立了街道峡谷内机动车尾气中颗粒物扩散模型,并给出了边界条件.采用标准k-ε模型与离散相模型对街道峡谷内部气流运动、颗粒物扩散及浓度分布进行了模拟计算,并计算了高架桥对风场及颗粒物扩散的影响.结果表明:H/W越大,街道峡谷内颗粒物浓度越高,同时颗粒物平均滞留时间越长.相对于没有高架桥的街道峡谷,高架桥附近区域风场变化明显,但对建筑物墙壁、地面及峡谷顶层处影响较小.街道峡谷内存在高架桥时,在墙壁较低处颗粒物浓度增加.