Nano Fe2O3 embedded in montmorillonite with citric acid enhanced photocatalytic activity of nanoparticles towards diethyl phthalate

Nano-Fe₂O₃ embedded in montmorillonite particles (Fe-Mt) were prepared to degrade diethyl phthalate (DEP) with citric acid (CA) under xenon light irradiation. Compared to pristine montmorillonite (Na-Mt), the embedding process increased 14.5-fold of iron content and 1.8-fold of specific surface area. The synthesized Fe-Mt have more oxygen vacancies than Fe₂O₃ nanoparticles (nFe₂O₃), which could induce more reactive oxygen species (ROSs) generation in the presence of CA under xenon lamp irradiation. Fe-Mt with CA enhanced photo-assisted degradation of DEP 2.5 times as compared to nFe₂O₃ with CA. Quenching experiments, electron paramagnetic resonance (EPR) spectroscopy and identification of products confirmed that surface-bound ?OH was the main radical to degrade DEP. Common anions (i.e., NO₃^?, CO₃^2?, Cl^?) and humic acid could compete ?OH with DEP and cause slower degradation of DEP. The removal efficiency of DEP was more than 56% with Fe-Mt after three recycles, and the dissolved Fe concentration from Fe-Mt was below 75 μmol/L, indicating Fe-Mt had a good stability as a catalyst. Fe-Mt together with CA appeared to be a promising strategy to remove organic pollutants in surface water, or topsoil under solar irradiation.     

Disentangling the effects of heterogeneity, stochastic dynamics and sampling in a community of aquatic insects

A dynamic and heterogeneous species abundance model generating the lognormal species abundance distribution is fitted to time series of species data from an assemblage of stoneflies and mayflies (Plecoptera and Ephemeroptera) of an aquatic insect community collected over a period of 15 years. In each year except one, we analyze 5 parallel samples taken at the same time of the season giving information about the over-dispersion in the sampling relative to the Poisson distribution. Results are derived from a correlation analysis, where the correlation in the bivariate normal distribution of log abundance is used as measurement of similarity between communities. The analysis enables decomposition of the variance of the lognormal species abundance distribution into three components due to heterogeneity among species, stochastic dynamics driven by environmental noise, and over-dispersion in sampling, accounting for 62.9, 30.6 and 6.5% of the total variance, respectively. Corrected for sampling the heterogeneity and stochastic components accordingly account for 67.3 and 32.7% of the among species variance in log abundance. By using this method, it is possible to disentangle the effect of heterogeneity and stochastic dynamics by quantifying these components and correctly remove sampling effects on the observed species abundance distribution.     

Formation of secondary inorganic aerosol in a frigid urban atmosphere

•Harbin showed relatively high threshold RH (80%) for apparent increase of SOR. •The observed SOR were at the lower end of the ratios from Beijing’s winter. •Temperature-dependent increase of NOR was sharper than that of SOR. • NOR increased with stronger biomass burning impact but SOR was largely unchanged. Formation of secondary inorganic aerosol (SIA) was investigated during a six-month long heating season in Harbin, China. Enhanced sulfate formation was observed at high relative humidity (RH), with the same threshold RH (80%) for both colder and warmer measurement periods. Compared to wintertime results from Beijing, the threshold RH was considerably higher in Harbin, whereas the RH-dependent enhancement of sulfur oxidation ratio (SOR) was less significant. In addition, the high RH events were rarely encountered, and for other periods, the SOR were typically as low as ~0.1. Therefore, the sulfate formation was considered inefficient in this study. After excluding the several cases with high RH, both SOR and the nitrogen oxidation ratio (NOR) exhibited increasing trends as the temperature increased, with the increase of NOR being sharper. The nitrate to sulfate ratio tended to increase with increasing temperature as well. Based on a semi-quantitative approach, this trend was attributed primarily to the temperature-dependent variations of precursors including SO₂ and NO₂. The influence of biomass burning emissions on SIA formation was also evident. With stronger impact of biomass burning, an enhancement in NOR was observed whereas SOR was largely unchanged. The different patterns were identified as the dominant driver of the larger nitrate to sulfate ratios measured at higher concentrations of fine particulate matter.     

Stabilization of potassium permanganate particles with manganese dioxide

A new potassium permanganate reagent with slow-release properties was designed and tested for possible application in in situ chemical oxidation. For this purpose, MnO₂-coated KMnO₄ particles (MCP) were prepared by partial reduction of solid KMnO₄ using the acid-catalyzed reaction with n-propanol or the comproportionation of Mn(VII) and Mn(II) in n-propanol as reaction medium. Column tests showed that, for MCP with a residual KMnO₄ fraction of 70 wt%, the duration of permanganate release under flow-through conditions was prolonged by a factor of 10 compared to untreated KMnO₄. While KMnO₄ is too soluble to be used in reactive barriers, MCP could be introduced into the aquifer by filling of trenches or boreholes; this would allow a prolonged passive dosing of permanganate into the flowing groundwater. In addition, experiments were conducted in order to determine the oxidation capability of native KMnO₄ particles and MCP in CH₂Cl₂, a representative non-polar non-aqueous phase liquid (NAPL). It may be possible to utilize the significantly higher reactivity of MCP under these conditions for the design of slow-release permanganate particles for NAPL source treatment.     

Heterogeneous uptake of gaseous hydrogen peroxide on mineral dust

The heterogeneous uptake processes of hydrogen peroxide on Arizona test dust and two types of authentic Chinese mineral dusts, i.e., Inner Mongolia desert dust and Xinjiang calciferous dust, were investigated using a Knudsen cell reactor coupled with a quadrupole mass spectrometer. The uptake coefficients were measured as a function of the initial concentration of H_2O_2 from 2.6 × 10~(11) to 1.2 × 10~(12)molecules/cm~3, and the temperature dependence of the uptake coefficients was investigated over a range from 253 to 313 K. The concentration of H_2O_2 showed little effect on the uptake coefficients of these heterogeneous processes. As a function of temperature, the initial uptake coefficients decrease with increasing temperature, whereas the steady state uptake coefficients of Arizona test dust and Inner Mongolia desert dust increase with increasing temperature. Implications for the understanding of the uptake processes onto mineral dust samples were also discussed.     

特别选题:环境微界面过程与污染控制序

长期以来,人们主要关注的是污染物的均相环境过程,这一点在大气污染化学和水污染化学的研究中尤其明显。然而近年来,人们开始关注环境中的非均相反应过程,从相对微观的尺度思考和探索环境的微界面问题,并从不同的视角不断认识和揭示这一过程在环境污染及其控制中的作用和意义。1997年,由荷兰科学家L.K.Koopal教授发起设立了Interfaces Against Pollution两年一次的系列国际会议,形成了全球范围内有关科学研究组织和科学家探讨和交流环境界面问题的重要平台。中国科学院生态环境研究中心汤鸿霄院士在我国首次提出环境微界面的概念,并于2003年主编了《环境科学学报》之“环境微界面过程研究论文专辑”,为该专辑作序并发表了“环境纳米污染物与微界面水质过程”的研究论文,对环境纳米微界面问题给出了全面和准确的内涵,进而开启了我国在此方面的系统性研究工作。基于汤鸿霄院士提出的环境微界面内涵和思想,2006年中国科学院生态环境研究中心组织了“环境微界面过程与污染控制”创新研究群体,得到国家自然科学基金委员会的资助。群体的研究目标是深入探索污染物在环境微界面的转移转化机制与控制原理,力争在复杂条件下微界面的定量化表征、污染物在环境微界面的转移转化规律及复合效应、基于微界面原理的环境过程调控等方面取得科学与技术突破。该研究群体的建立及深入开展相关的研究工作,将有力推动我国环境微界面理论和技术的研究进展,也将不断培养本研究方向的专业化高级人才。在过去的2年里,该研究群体在不同环境微界面特征及过程表达、污染物在典型介质和界面变化行为的原位观测、水/气/土/生物微界面上污染物的转移转化规律、基于微界面过程的水、气、固等环境的污染控制等方面取得预期研究进展。本专栏所组织的稿件,即试图从不同角度反映我们所关注的环境微界面研究领域,并通过前期研究所获得的一些具体的科学数据和结果,对环境微界面过程给出进一步的认识。然而,由于本群体的研究工作还不够深入,这样一个专栏所发表的内容不论是对环境微界面的概念与内涵,还是在探索与创新上,都还是初步的和不成熟的。或者说,本专栏所反映的只是一个有待发展和完善的科学思路。由于本专栏作者水平有限,这些论文定有不少谬误之处,敬请读者批评指正。 衷心感谢《环境科学学报》编辑部为我们提供这样一个重要的平台和机会,感谢他们为本专栏组稿、编辑和出版所做出的辛苦努力！     

Measurement and analysis of non-Fickian dispersion in heterogeneous porous media

Contaminant breakthrough behavior in a variety of heterogeneous porous media was measured in laboratory experiments, and evaluated in terms of both the classical advection-dispersion equation (ADE) and the continuous time random walk (CTRW) framework. Heterogeneity can give rise to non-Fickian transport patterns, which are distinguished by "anomalous" early arrival and late time tails in breakthrough curves. Experiments were conducted in two mid-scale laboratory flow cells packed with clean, sieved sand of specified grain sizes. Three sets of experiments were performed, using a "homogeneous" packing, a randomly heterogeneous packing using sand of two grain sizes, and an exponentially correlated structure using sand of three grain sizes. Concentrations of sodium chloride tracer were monitored at the inflow reservoir and measured at the outflow reservoir. Breakthrough curves were then analyzed by comparison to fitted solutions from the ADE and CTRW formulations. In all three systems, including the "homogeneous" one, subtle yet measurable differences between Fickian and non-Fickian transport were observed. Quantitative analysis demonstrated that the CTRW theory characterized the full shape of the breakthrough curves far more effectively than the ADE.     

Infiltration and redistribution of LNAPL into unsaturated layered porous media

Enhanced understanding of light non-aqueous phase liquid (LNAPL) infiltration into heterogeneous porous media is important for the effective design of remediation strategies. We used a 2-D experimental facility that allows for visual observation of LNAPL contours in order to study LNAPL redistribution in a layered porous medium. The layers are situated in the unsaturated zone near the watertable and they are inclined to be able to observe the effect of discontinuities in capillary forces and relative permeabilities. Two experiments were performed. The first experiment consisted of LNAPL infiltration into a fine sand matrix with a coarse sand layer, and the second experiment consisted of a coarse sand matrix and a fine sand layer. The numerical multi-phase flow model STOMP was validated with regard to the experimental results. This model is able to adequately reproduce the experimental LNAPL contours. Numerical sensitivity analysis was also performed. The capillarity contrast between sands was found to be the main controlling factor determining the final LNAPL distribution.     

Effect of phosphate on heterogeneous Fenton oxidation of catechol by nano-Fe3O4: Inhibitor or stabilizer?

The effect of phosphate on adsorption and oxidation of catechol, 1,2-dihydroxybenzene, in a heterogeneous Fenton system was investigated. In situ attenuated total reflectance infrared spectroscopy (ATR-FTIR) was used to monitor the surface speciation at the nano-Fe₃O₄ catalyst surface. The presence of phosphate decreased the removal rate of catechol and the abatement of dissolved organic compounds, as well as the decomposition of H₂O₂. This effect of phosphate was mainly due to its strong reaction with surface sites on the iron oxide catalyst. At neutral and acid pH, phosphate could displace the adsorbed catechol from the surface of catalyst and also could compete for surface sites with H₂O₂. In situ IR spectra indicated the formation of iron phosphate precipitation at the catalyst surface. The iron phosphate surface species may affect the amount of iron atoms taking part in the catalytic decomposition of H₂O₂ and formation of hydroxyl radicals, and inhibit the catalytic ability of Fe₃O₄ catalyst. Therefore, phosphate ions worked as stabilizer and inhibitor in a heterogeneous Fenton reaction at the same time, in effect leading to an increase in oxidation efficiency in this study. However, before use of phosphate as pH buffer or H₂O₂ stabilizer in a heterogeneous Fenton system, the possible inhibitory effect of phosphate on the actual removal of organic pollutants should be fully considered.     

Gas-phase thermal explosions in catalytic direct oxidation of alkenes

The metal-based catalytic oxidation of alkenes to the corresponding epoxides is playing a significant role in the modern chemical industry. Nevertheless, these key processes are still lacking proper understanding with respect to the gas-phase runaway behaviour (thermal explosion) and to the hot spot formation on the catalytic surface, under the typical process conditions.This work aims to enlighten these aspects by considering either the catalytic or the gas-phase chemistry for the development of reactor operative diagrams, in order to define the best-operating conditions with respect to the selectivity, the productivity, and the process safety aspects.The proposed methodology has been applied to the oxidation of ethylene and propylene for the direct oxidation process by pure oxygen, considering a detailed kinetic model accounting for the homogeneous reactions, coupled with the heterogeneous catalytic mechanisms.Sensitivity and reaction path analyses were performed to individuate the ruling species and reactions determining the transition to runaway conditions.