Dense Nonaqueous Phase Liquid Tracer Tests: Experimental Results

Two dense nonaqueous phase liquid (DNAPL) tracer tests werecarried out in a shallow aquifer north of Fort Worth, TX. i-Propanolwas used as the nonpartitioning tracer; n-hexanol and n-octanol werethe partitioning tracers. Field data, mathematical modeling, theresults of column tests, and field tracer tests with NaCl were usedin designing the DNAPL tracer tests. The results indicated the presenceof DNAPL at both sites tested; semi-quantitative estimates of theamounts of DNAPL present were obtained by mathematical modeling.Interpretation was complicated by heterogeneity of the aquifer andmass transport effects.     

Evaluation of thermal properties and process hazard of three ionic liquids through thermodynamic calculations and equilibrium methods

Industrial and new energy applications of ionic liquids (ILs) may have to be used at high temperatures conditions, such as in batteries and fuel applications, which may cause thermal hazards. However, there are few studies on the thermal hazards of ILs. To ensure the thermal safety of ILs processes, three commonly used ILs were selected for analysis: 1-butyl-3-methylimidazolium nitrate ([Bmim]NO₃), 1-butyl-2,3-dimethylimidazolium nitrate ([Bmmim]NO₃), and 1,3-dimethylimidazolium nitrate ([Mmim]NO₃). The process hazards under adiabatic conditions demonstrated that [Bmmim]NO₃ and [Mmim]NO₃ have extensive explosion hazards. The self-reaction characteristics determined by the isothermal test indicated that the ILs are nth reactions, and the thermal decomposition features were also determined by thermogravimetric analysis. The data were obtained with a nonlinear thermodynamic model and used to establish the basic thermal hazards of the three ILs. In addition, based on the thermal equilibrium theory, the critical safety parameters can be inferred. The effects of heat transfer in 25.0 g and 50.0 g containers were discussed. The results show that [Mmim]NO₃ will produce a thermal runaway reaction at a lower temperature (<100 °C) and has the shortest reaction time (<1 day), which means [Mmim]NO₃ is considered to be the most hazardous material among the three ILs studied.     

咪唑类[PF6]^-型离子液体萃取胺类化合物

以眯唑类[PF6]^-型离子液体1-丁基-3-甲基咪唑六氟磷酸盐（[Bmim][PF6]）、1-己基-3-甲基咪唑六氟磷酸盐（[Hmim][PF6]）和1-辛基-3-甲基咪唑六氟磷酸盐（[Omim][PF6]）对苯胺、对氯苯胺等7种胺类化合物的萃取，考察了溶液初始浓度、相比、盐类、pH及离子液体眯唑基团上取代烷基对萃取平衡的影响，并研究了萃取过程的热效应。实验结果表明：溶液初始浓度对分配系数影响较小；相比10：1是离子液体对胺类化合物的溶解饱和临界点，当相比大于10：1时，分配系数降低；NaCl、K2SO4可以增大萃取分配系数，ZnSO4对分配系数几乎没有影响；pH增加，分配系数增大；离子液体对不同取代基的胺类萃取能力有较大的差异，咪唑基团上取代烷基的长度对不同胺类物质的分配系数影响较显著；萃取过程属于焓增大的吸热过程。     

Relevant parameters for assessing the environmental impact of some pyridinium, ammonium and pyrrolidinium based ionic liquids

Several physico-chemical properties relevant to determine the environmental impact of ionic liquids - aqueous solubility, octanol/water partition coefficient, chromatographically derived lipophilicity and infinite dilution diffusion coefficients in water - were measured in ionic liquids based on pyridinium, ammonium and pyrrolidinium cations with bis(trifluoromethylsulfonyl)imide anions. The influence of the presence of hydroxyl or ester groups in the physico-chemical properties of these liquids was checked. It appeared that the presence of functional oxygenated moieties reduces the lipophilicity of ionic liquids and so decreases the risk of bioaccumulation in environment.     

Expression alterations of cytochromes P4501A1, 2E1, and 3A,and their receptors AhR and PXR caused by 1-octyl-3-methylimidazolium chloride in mouse mammary carcinoma cells

Cytochrome P450s (CYPs) play a key role in the metabolism of a wide range of environmental xenobiotics and endogenous compounds. The expression and activity levels of CYPs can be elevated by a process of induction involving the activation of nuclear receptors. The effects of the ionic liquid 1-octyl-3-methylimidazolium chloride ([C₈mim][Cl]) on the expression of cytochrome P450 members, including CYP1A1, CYP2E1, and CYP3A, as well as on aryl hydrocarbon receptor (AhR) and pregnane X receptor (PXR) in mouse mammary carcinoma cells (EMT6) were investigated by using quantitative real-time PCR in the present study. The results reveal that [C₈mim][Cl]-exposure up-regulates the expressions of CYP1A1, CYP2E1, and CYP3A at mRNA level, suggesting that imidazolium-based ionic liquids can activate CYPs. Our results also suggest that [C₈mim][Cl]-mediated CYP3A induction be PXR-dependent. This result may be beneficial to evaluating the environmental toxicity of imidazolium-based ionic liquids and investigating the metabolism of imidazolium-derivative drugs.     

负载咪唑型离子液体硅胶吸附材料制备及应用研究

制备了3种取代咪唑键合的硅胶负载型离子液体(甲基咪唑-SIL、氨丙基咪唑-SIL及十二烷基咪唑-SIL),比较了其对水中双酚A(BPA)的吸附能力。在该研究的实验条件下,BPA在十二烷基咪唑-SIL与水溶液之间的分配系数K_d值高达(2.58±0.02)×10³ L/kg,氨丙基咪唑-SIL、甲基咪唑-SIL的K_d值也分别达到(2.26±0.28)×10、(2.71±0.16)×10 L/kg。采用甲醇为洗脱液,可以对十二烷基咪唑-SIL相中的BPA进行有效回收,2次洗脱的合并回收率为106.7%±4.8%。以十二烷基咪唑-SIL作为被动采样装置的接收相,对污水处理厂出水中BPA进行了被动采样监测应用的微宇宙实验研究。结果表明,在实验周期内,十二烷基咪唑-SIL被动采样器对水体中BPA的被动采集呈线性,其采集速率为0.33 L/d,与以HLB为接收相的商品化被动采样器接近,并且同HLB固相萃取填料相比,离子液体接收相对BPA的采集更具选择性,基质效应较小,可作为被动采样监测装置的理想接收相材料。     

离子液体萃取法回收废水中的醋酸丁酯

利用离子液体1-己基-3-甲基咪唑六氟磷酸盐萃取模拟废水中的醋酸丁酯。萃取液经减压蒸馏回收醋酸丁酯，离子液体也得到再生。实验结果表明:萃取率随废水与离子液体体积之比(相比)的增加而减小，随萃取时间的延长而增大，随萃取温度的升高而增大;在相比为6∶1、萃取时间为40min、萃取温度为50℃的条件下，萃取率达98.98%，醋酸丁酯纯度达99.8%;回收后离子液体可重复使用且萃取率基本不变。     

Solvent tolerant marine bacterium Bacillus aquimaris secreting organic solvent stable alkaline cellulase

The organic solvent tolerant bacteria with their physiological abilities to decontaminate the organic pollutants have potentials to secrete extracellular enzymes of commercial importance. Of the 19 marine bacterial isolates examined for their solvent tolerance at 10 vol.% concentration, one had the significant tolerance and showed a relative growth yield of 86% for acetone, 71% for methanol, 52% for benzene, 35% for heptane, 24% for toluene and 19% for ethylacetate. The phylogenetic analysis of this strain using 16S rDNA sequence revealed 99% homology with Bacillus aquimaris. The cellulase enzyme secreted by this strain under normal conditions showed an optimum activity at pH 11 and 45 °C. The enzyme did show functional stability even at higher pH (12) and temperature (75 °C) with residual activity of 85% and 95% respectively. The enzyme activity in the presence of different additives were in the following order: Co⁺² > Fe⁺² > NaOCl₂ > CuSO₄ > KCl > NaCl. The enzyme stability in the presence of solvents at 20 vol.% concentration was highest in benzene with 122% followed by methanol (85%), acetone (75%), toluene (73%) and heptane (42%). The pre-incubation of enzyme in ionic liquids such as 1-ethyl-3-methylimidazolium methanesulfonate and 1-ethyl-3-methylimidazolium bromide increased its activity to 150% and 155% respectively. The change in fatty acid profile with different solvents further elucidated the physiological adaptations of the strain to tolerate such extreme conditions.     

嗅觉标准液的人群测试

嗅觉标准液是可使人的嗅觉阈值测试标准化，科学化，数量化，应用嗅觉标准液对人群的嗅觉阈值测试，可以了解我国人群嗅觉状及特点，以便应用标准液筛选嗅觉试验员和鼻科临床无创伤检验等方面。     

Toxicity of various anions associated with methoxyethyl methyl imidazolium-based ionic liquids on Clostridium sp

We investigated the effects on the growth of the anaerobic bacterium, Clostridium sp., of the ionic liquid, 1-methoxyethyl-3-methyl imidazolium [MOEMIM]⁺, derived from imidazolium cation and paired with one of a variety of counter-ions, viz., tetrafluoroborate [BF₄]^-, hexafluorophosphate [PF₆]^-_, trifluoroacetate [CF₃COO]^-, bis(trifluoromethane)sulfonamide [Tf₂N]^-, methane sulfonate [OMS], and 1-butyl-3-methyl imidazolium tetrafluoroborate [BMIM][BF₄]. These anions, in association with [MOEMIM]⁺ lowered the growth rate of the bacterium, showing the following trend: [Tf₂N]^- ≧ [PF₆]^- > [BF₄]^- > [CF₃COO]^- > [OMS]⁻. Anions incorporating fluorine were more toxic than those without it, and their toxicity rose with an increase in the number of fluorine atoms. Also, [MOEMIM]⁺[BF₄]^- was less toxic than [BMIM]⁺[BF₄]^-, probably due to the presence of a methoxyethyl functional group integrated in the cation side chain.