DNAPL remediation with in situ chemical oxidation using potassium permanganate. Part I. Mineralogy of Mn oxide and its dissolution in organic acids

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 A. The chemical formula is K(0.854)Mn(1.786)O(4).1.55H(2)O. It has a relatively small specific surface area at 23.6+/-0.82 m(2)/g. Its point of zero charge (pzc) was measured as 3.7+/-0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m(2)/h for citric acid, 1.35 mM/m(2)/h for oxalic acid, and 5.176 mM/m(2)/h for EDTA. These rates compare with 0.0025 mM/m(2)/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant potential in using these organic acids to remove precipitates formed during the oxidation reaction.     

Adsorption of phenol on inorganic-organic pillared montmorillonite in polluted water

Both inorganic- and organic-pillared montmorillonites (PMts) were used to adsorb phenol to study suitable conditions for adsorption and adsorption isotherms. The adsorbing capacity of modified clays depends not only surface area, but mainly on micropore structure and surface components. After incandescing at 500 degrees C, the pillar structure and the basal interlayer spacing (1.83 nm) remained stable. Using modified PMt with surfactant can improve adsorbing capacity greatly. The PMt can be recycled, and it is a potential substance for adsorption of environmental pollutants.     

Enhanced photocatalytic degradation of VOCs using Ln3+-TiO2 catalysts for indoor air purification

Two types of lanthanide ion-doped titanium dioxide (Ln3+-TiO2) catalysts including La3+-TiO2 and Nd3+-TiO2 were prepared by a sol-gel method. The effects of the lanthanide ion doping on the crystal structure, surface area, adsorption properties, pore size distribution, and surface chemical state of the catalysts were investigated by means of XRD, BET, and XPS. As results, the crystal size decreased significantly, while the specific surface area, t-plot total surface area, micropore volume, and the total pore volume increased owing to the lanthanide ion doping. The nitrogen adsorption-desorption isotherms of the catalysts showed that the N2 adsorption ability of the Ln3+-TiO2 catalysts was better than the TiO2 catalyst. Among them, the 0.7% Ln3+-TiO2 catalysts demonstrated the highest adsorption ability. The photocatalytic activity of the catalysts was investigated in the experiments of the photocatalytic degradation of benzene, toluene, ethylbenzene and o-xylene (BTEX) in a gaseous phase. The photocatalytic efficiency of the TiO2 catalysts with the lanthanide ion doping was remarkably enhanced by BTEX removal. The 1.2% Ln3+-TiO2 catalysts achieved the highest photocatalytic activity. The enhanced photodegradation of BTEX is possibly due to the improved adsorption ability and the enhanced electron-hole pairs separation due to the presence of Ti3+ on the surface of Ln3+-TiO2 catalysts and the electron transfer between the conduction band/defect level and lanthanide crystal field state.     

Bioconcentration of cadmium in water hyacinth (Eichhornia crassipes) in relation to thiol group content

To study the bioconcentration of cadmium in water hyacinth, the plants were exposed to water containing 2 microg Cd2+/ml for extended periods of time. Three strains from several exposures during a 30-day period were sampled for the analyses of cadmium and thiol group. The data showed that the plant concentrates cadmium mainly in the roots and that the cadmium uptake is proportional to the increase of the thiol group content. The latter suggests the possibility of using the thiol group content to assess the bioconcentration of heavy metal ions in water hyacinth and as a general parameter for monitoring the heavy metal pollution of water. A simple two-compartmental model was used to simulate the kinetics of cadmium uptake. The calculated bioconcentration factor matches the one derived directly from experimental data, indicating the adequacy of the model.     

上海近30年人为热变化及与气温的关系研究

为研究上海人为热,根据统计年鉴资料,估算了1978～2008年工业、民用和机动车人为热的排放量及其总和,并从时间变化和空间分布两个方面进行分析。鉴于人为热对温度的影响,根据上海地区11个区县气象观测站近30 a的年平均气温资料,研究城郊气温及其差值与人为热变化的关系。结果表明：(1)近30 a来,上海工业、民用和机动车人为热排放量及其总和呈现逐年上升的趋势。2000年前上海人为热缓慢增长;而2000年后(含2000年)则呈现快速增长的趋势。(2)工业是上海人为热的主要来源,但自1978年以来,工业人为热比重逐年下降。2000年起,机动车人为热比重超过民用人为热。(3)上海工业人为热排放主要分布在以宝钢为主的宝山长江沿岸地区、黄浦江沿岸市区段地区、以吴泾为主的闵行南部地区,以及金山石化地区。而民用和机动车人为热排放主要集中在市区。(4)自20世纪90年代以后,市中心与郊区的气温差加大,城市热岛效应强度日趋增强。同时,上海地区温度的空间分布特征与人为热的空间分布有很好的一致性。人为热的大量排放对气温的增加也是不可忽视的重要因素     

Changes in distribution patterns of weed species richness in agricultural lands on Qinghai-Tibet Plateau under climate change北大核心CSCD

农田杂草是阻碍农业生产的主要因素之一.明确农田杂草丰富度分布格局对农业生产管理具有重要意义.以青藏高原农田杂草为研究对象,利用物种分布模型探讨基于县域尺度的农田杂草物种丰富度分布格局及其未来(2050s)的变化,利用逐步回归筛选影响物种丰富度的环境因子,基于传统最小二乘法(OLS)和地理加权回归模型(GWR)分析环境因子对农田杂草物种丰富度的影响,并对两种分析方法进行比较.结果显示:(1)分布在青藏高原的农田主要杂草有51科284种,其中59种单子叶杂草、222种双子叶杂草、135种一年生杂草和149种多年生杂草.青藏高原农田杂草物种丰富度呈由西向东递增的变化规律,物种丰富度中心(丰富度值为167-194)主要集中在一江两河、河湟谷地和川西北等地区;(2)全球气候变化背景下,未来(2050s)青藏高原农田杂草物种丰富度整体呈由东南向西北方向增加的趋势,其中SSP1-2.6情境下最多增加43种,SSP5-8.5情境下最多增加49种;(3)GWR模型优于OLS,其结果表明青藏高原农田杂草物种丰富度的主要驱动因子是最冷季平均温、太阳辐射和最干月降水量,上述变量对杂草丰富度的影响存在明显的空间差异性,其中最冷季平均温由南向北逐渐从负向影响转变为正向影响.太阳辐射整体在青藏高原东部边缘等地区对农田杂草丰富度起正向的影响,在藏东南、青藏高原北部边缘等地区起负向的影响.最干月降水量对整个研究区域起负向影响,并表现出影响力由南向北逐步递增的趋势.上述结果表明青藏高原农田杂草物种丰富度调查不足,实际观测到的丰富度值明显低于当前气候下潜在的丰富度值,存在低估现象.当前气候背景下的农田杂草物种丰富度中心分布地区在未来仍是重点监管对象,且未来青藏高原部分地区作物可能面临新的杂草入侵风险.建议未来研究应注重于青藏高原粮食主产区农田杂草群落结构和功能调查、杂草和作物种间关系、耕地尺度上丰富度驱动因子分析等方面,为区域杂草管理和防治提供充分科学依据.(图6表2参53)     

Groundwater and Nutrient Discharge into Jiaozhou Bay,North China

The health of near shore marine ecosystems has long been a concern because of its importance to coastal areas. Jiaozhou Bay (JZB) is one such marine ecosystem experiencing rapid water quality degradation in the last several decades. From the area surrounding the bay, the nutrients discharged into the bay through surface water and groundwater has been greatly changed. The thickness of the aquifers and the permeability is relatively high, the concentrations of nutrients in the groundwater are generally high, and so the groundwater discharged into JZB is very significant. However, no attempt has ever been made to evaluate the amount of nutrients discharged into the bay area via groundwater. In this study, the cross-section method and water balance method were used to estimate the amount of groundwater and nutrients discharged into JZB via the subsurface. Groundwater was monitored and sampled at aquifers surrounding the bay area, and some previously available data was also analyzed. The results indicated that groundwater from the Baisha Aquifer east of JZB now is the major source of nutrients (nitrate, dissolved SiO₂) being discharged into the bay. The concentrations of nutrients in the groundwater have been increasing with intensive agricultural land use. However, Dagu Aquifer, the largest aquifer north of JZB, only provides limited nutrients to the bay area because of the construction of a low permeability subsurface dam. Historically, during the 1970s to the 1990s, the Baisha Aquifer experienced seawater intrusion due to excessive groundwater withdrawal. The same was true for the Dagu Aquifer from the 1980s to the 1990s. Because of this, no significant nutrients were discharged into the bay.     

Effect of Florasulam on soil residues and enzyme activity of wheat in drylands北大核心CSCD

Florasulam is a three azole and pyrimidine sulfonamide herbicide, mainly used for weeds prevention and control in winter wheat fields. The main purpose of this experiment was to study the effects of different doses of Florasulam on soil residues and on the enzymatic activity of wheat cultivated in drylands, and to provide the theoretical basis for a scientific use of florasulam. Five doses (0, 15, 30, 45, and 60 mL/667 m2) of Florasulam were applied in order to detect differences in soil residue content and enzymatic activities. Soil residues and enzymatic activities (catalase, phosphatase, urease, dehydrogenase) were measured and analyzed after the 5 different doses of Florasulam were processed. The residual amount of Florasulam in the soils decreased gradually with the growth phase of wheat, and was lower than that of 0.01 mg/kg. The residual amount of Florasulam in different soil layers gradually decreased with the increase of soil thickness. The enzymatic activity of soils treated with Florasulam was basically T3 > T2 > T1 > CK > T4, where T3 was the highest, whereas T4 could inhibit the enzymatic activity. Under these experimental conditions, in order to decrease soil pollution and lower Florasulam residues, it is recommended to apply Florasulam at a concentration range of 30 to 45 mL/667 m2 © 2018 Science Press. All rights reserved.