土壤复合污染条件下对二氯苯和重金属吸附行为与生态毒性

环境污染问题实际上是多种污染物共存引起的复合污染。多元体系复合污染条件下的交互作用，特别是有机与无机污染物复合污染，使得污染物在土壤中的环境行为、联合生态毒性效应及其发生机制变得更加复杂、更加不可预测。由于疏水性有机污染物（HOCs）和重金属在理化性质上存在极大差异，致使开展HOCs-重金属复合体系下，污染物的土壤环境行为和毒性效应机制的研究还存在一定的难度，这方面的研究也还不多。 本研究选择了典型的HOCs对二氯苯（1,4-DCB）和土壤中典型有毒重金属元素Cd、Cu为研究对象，着重分析共存污染物的存在对其各自环境吸附行为的影响及其作用规律；并开展了二者复合污染对土壤酶系统、土壤-植物复合生态系统的联合生态毒性效应的研究。 Cd、Cu的存在对1,4-DCB在棕壤和黑土上的吸附产生了竞争抑制作用，增加了其向土壤环境中的释放。其中，Cu的抑制程度高于Cd，老化Cd的抑制程度要高于未老化Cd。而1,4-DCB对Cd、Cu在两种土壤的吸附能力基本没有产生影响，但降低了Cd的解吸滞后性系数，对Cu的解吸影响较小。 1,4-DCB和Cd在土壤中的存在具有一定的生态风险，多数情况下抑制土壤脱氢酶和脲酶活性。 二者联合毒性类型表现复杂：低浓度1,4-DCB（50 mg kg-1）和Cd复合污染主要产生协同效应，而高浓度（100 mg kg-1）则产生协同、拮抗以及加和作用，与其浓度组合、土壤持留时间及酶种类有关。因此，用土壤酶活性变化作为指标来定量表征二者复合污染所引起的土壤环境质量变化还存在一定难度。 在土壤-植物复合系统中，不同植物叶片和根系具有不同的对抗污染物氧化胁迫的生理生化机制，各抗氧化剂会协同对抗，表现出不同的氧化损伤效应。1,4-DCB与Cd对植物膜脂质过氧化和抗氧化酶系统的联合毒性效应不仅与其浓度组合有关，还与植物种类以及受试部位有关。二者单一与复合处理均导致大豆叶片和小麦根部MDA含量升高，表明氧化胁迫作用的存在。因此，大豆叶片和小麦根部中MDA含量增加似乎更能反映其受污染物胁迫的程度。 采用多隔层根际箱方法，研究了1,4-DCB与Cd对不同植物根际各毫米级微域土壤酶活性的联合毒性效应。在相同浓度水平下，二者对大豆和小麦根际各级微域土壤酶活性的影响不一致，随根际距离增加，酶活性没有呈现一致的变化趋势。总的来说，二者联合胁迫下，大豆近根际区域（特别是1mm）土壤脲酶活性受到诱导，而小麦中央区域和1、2mm近根际区域土壤脱氢酶活性则被抑制。

Biosorption of uranium by chemically modified Rhodotorula glutinis

The present paper reports the biosorption of uranium onto chemically modified yeast cells, Rhodotorula glutinis, in order to study the role played by various functional groups in the cell wall. Esterification of the carboxyl groups and methylation of the amino groups present in the cells were carried out by methanol and formaldehyde treatment, respectively. The uranium sorption capacity increased 31% for the methanol-treated biomass and 11% for the formaldehyde-treated biomass at an initial uranium concentration of 140 mg/L The enhancement of uranium sorption capacity was investigated by Fourier transform infrared (FTIR) spectroscopy analysis, with amino and carboxyl groups were determined to be the important functional groups involved in uranium binding. The biosorption isotherms of uranium onto the raw and chemically modified biomass were also investigated with varying uranium concentrations. Langmuir and Freundlich models were well able to explain the sorption equilibrium data with satisfactory correlation coefficients higher than 0.9. (C) 2010 Elsevier Ltd. All rights reserved.

Hydrothermal stability and catalytic activity of aluminum-containing mesoporous ethane-silicas

Aluminum was incorporated into the mesoporous framework of ethane-silica by one-pot condensation of Al(OiPr)(3) with 1,2-bis(trimethoxysilyl)ethane using octadecyltrimethylammonium chloride as surfactant. Powder X-ray diffraction patterns, nitrogen sorption analysis, and TEM results reveal the formation of an ordered mesoporous material with uniform porosity. Al-27 MAS NMR confirms the incorporation of aluminum in the framework. The synthesized materials exhibit extremely high hydrothermal stability in boiling water (no obvious change of mesostructure and textural properties was observed even after refluxing in water for 100 h), which could be mainly contributed to the ethane-bridged mesoporous framework. The aluminum-containing mesoporous ethane-silicas are efficient catalysts for the alkylation of 2,4-di-tert-butylphenol by cinnamyl alcohol to yield a flavan.

Direct synthesis of Al-SBA-15 mesoporous materials via hydrolysis-controlled approach

Aluminum-substituted mesoporous SBA-15 (Al-SBA-15) materials were directly synthesized by a hydrolysis-controlled approach in which the hydrolysis of the silicon precursor (tetraethyl orthosilicate, TEOS) is accelerated by fluoride or by using tetramethyl orthosilicate (TMOS) as silicon precursor rather than TEOS. These materials were characterized by powder X-ray diffraction (XRD), N-2 sorption isotherms, TEM, Al-27 MAS NMR, IR spectra of pyridine adsorption, and NH3-TPD. It is found that the matched hydrolysis and condensation rates of silicon and aluminum precursors are important factors to achieve highly ordered mesoporous materials. Al-27 MAS NMR spectra of Al-SBA-15 show that all aluminum species were incorporated into the silica framework for the samples prepared with the addition of fluoride. A two-step approach (sol-gel reaction at low pH followed by crystallization at high pH) was also employed for the synthesis of Al-SBA-15. Studies show that the two-step approach could efficiently avoid the leaching of aluminum from the framework of the material. The calcined Al-SBA-15 materials show highly ordered hexagonal mesostructure and have both Bronsted and Lewis acid sites with medium acidity.

Biosorption of Cd2+, Cu2+, Ni2+ and Zn2+ ions from aqueous solutions by pretreated biomass of brown algae

In this paper, marine brown algae Laminaria japonica was chemically modified by crosslinking with epichlorohydrin (EC1 and EC2), or oxidizing by potassium permanganate (PC), or crosslinking with glutaraldehyde (GA), or only washed by distilled water (DW). They were used for equilibrium sorption uptake studies with Cd2+, Cu2+, Ni2+ and Zn2+.

Constructing channel structures based on the assembly of p-sulfonatocalix[4]arene nanocapsules and [M(bpdo)(3)](2+)(M = Cu, Zn)

Novel channel structures based on [M(bpdo)(3)](2+) and p-sulfonatocalix[4]arene nanocapsules have been established; these are sustained exclusively by charge-assisted pi...pi interactions and sorption experiments show the porous materials have selective guest sorption properties.