NAPLs污染物指进锋面形态的指间距离预测

选取4种不同性质的NAPLs(非水相流体)污染物,分别应用分形维数方法和毛细压力函数方法对NAPLs迁移过程中有效界面张力和指进过程中指间距离的大小进行预测,同时建立二维可视化砂箱模型,模拟污染物在多孔介质中的非稳态指进迁移过程,获得指进迁移形态影像75幅. 结果表明,与试验观测值比较,对于相同迁移过程中的指间距离,毛细压力函数方法预测误差绝对值介于1%~93%,分形维数方法预测误差绝对值介于2%~25%,分形维数方法的预测误差小于毛细压力函数方法. 毛细压力函数方法对指间距离的预测随着NAPLs密度的增加而增大,对DNAPLs(重非水相流体)的预测误差明显增加,更适用于预测密度与水的密度相差不大的物质;分形维数方法的预测值与观测值呈显著线性相关(R2=0.957),相比于传统毛细压力函数方法,分形维数方法对指间距离的预测更准确,更适合用来预测不同密度NAPLs污染物的指进距离参数.      

Process hazard assessment of energetic ionic liquid with kinetic evaluation and thermal equilibrium

With the continuous development of battery technology, there are new research investments in materials of various parts. In the field of electrolytes, ionic liquids (IL) are considered to be excellent electrolytes and have been widely studied in distinct energy fields. However, it is necessary to pay attention to the safety characteristics of ionic liquids at high temperature due to the application of energy, but there is little research on the reaction and kinetics of ionic liquids. To ensure the safety of ionic liquids, such as high temperature, the common ionic liquid 1-Ethyl-3-methylimidazolium nitrate ([Emim] NO₃) was selected for analysis. The exothermic mode is obtained from the data of differential scanning calorimetry. The basic reaction parameters of [Emim] NO₃ were determined with thermodynamic equation simulation. For ionic liquids in the actual situation, consider adding a heat balance model to estimate its temperature change pattern and find out the hazard temperature and related safety parameters. Temperature changes were estimated by constructing 25.0 g and 50.0 g packages to simulate material reactions and heat transfer in the external environment. The results showed that [Emim] NO₃ had shorter TMR_ad and TCL (<1 day) when the temperature was above 180 °C.     

Toxicity of imidazolium- and pyridinium-based ionic liquids and the co-metabolic degradation of N-ethylpyridinium tetrafluoroborate

We examined the effects of the ionic liquids (ILs), 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF₆], N-ethylpyridinium tetrafluoroborate [EtPy][BF₄], and N-ethylpyridinium trifluoroacetate [EtPy][CF₃COO] on Pseudomonas fluorescens, a ubiquitous soil bacterium. In the presence of 0.5- and 1% of [BMIM][PF₆] or [EtPy][CF₃COO] the growth of bacteria was inhibited, whereas exposing them to 1% [EtPy][BF₄] increased the lag period wherein bacteria adapt to growth conditions before continuing to grow. However, at higher concentrations (5% and 10%), no growth was observed. The inhibitory effects were evident by a decrease in the optical density of the culture, a decline in the consumption of the carbon source, citric acid, and a change in the size of the bacterium. At concentrations below 1%, [EtPy][BF₄] was metabolized by P. fluorescens in the presence of citric acid. Oxidation of the side alkyl-chain of [EtPy][BF₄] caused the accumulation of N-hydroxylethylpyridinium and pyridinium as major degradation products.     

咪唑类离子液体的二氧化硫吸附性能

为研究咪唑类离子液体脱除烟道气中SO2的规律,以1-丁基,3-甲基氯代咪唑([Bmim]Cl)、1-丁基,3-甲基硝酸咪唑([Bmim]NO3)、1-丁基,3-甲基氟硼酸咪唑([Bmim]BF4)和1-戊基,3-甲基氯代咪唑([C5mim]Cl)4种离子液体作为SO2吸附剂,研究了不同条件下4种离子液体对模拟烟道气中SO2的吸附性能,并初步进行了离子液体再生脱硫试验.利用傅立叶变换红外光谱(FTIR)对吸附前、后和再生后的[Bmim]Cl结构变化进行了研究.结果表明,4种离子液体对SO2均有吸附能力,且吸附能力为:[C5mim]Cl[Bmim]Cl[Bmim]NO3[Bmim]BF4,其中[C5mim]Cl的累积脱硫量达到200.8mg/g,[Bmim]Cl的最佳脱硫温度为40.0℃;3种阴离子对脱硫性能的影响顺序为:Cl-NO3-BF4-.在温度为90.0℃、压强为0.09MPa、再生4.0h后,[Bmim]Cl的硫容从再生前的65.9mg/g下降到26.5mg/g.脱硫过程中离子液体的结构发生了变化,它对SO2分子同时存在物理吸附和化学吸附.     

A pore-scale investigation of mass transport from dissolving DNAPL droplets

Spheres and pendular rings of trichloroethylene and tetrachloroethylene are observed dissolving in an artificial porous medium consisting of a single layer of glass beads. Given the simple geometry of the droplets, pore-scale mass transfer coefficients are calculated. For dissolving spheres, mass transfer coefficients are found to be constant over time. However, coefficients for pendular rings are found to decrease as the rings shrink in size. This is consistent with the concept of diffusion-controlled mass transfer in low-flow zones. Sherwood numbers measured at Reynolds numbers between 0.0033 and 8.33 show a similar trend to empirical relationships established by previous researchers using other techniques. As in previous experiments, considerable scatter in mass transfer rates is observed at a given mean flux. It is hypothesized that this variation in local mass transfer rates is caused by variations in local pore velocity.     

溴化1-十四烷基-3-甲基咪唑对小鼠的肝脏毒性及其作用机制

研究离子液体溴化1-十四烷基-3-甲基咪唑盐([C₁₄mim]Br)对小鼠的肝脏毒性及其作用机制。实验设立3个剂量的染毒组(1/16 LD₅₀、1/8 LD₅₀、1/4 LD₅₀)和1个空白对照组,考察昆明种小鼠染毒14 d后,[C₁₄mim]Br对小鼠血清生化指标、肝脏抗氧化酶活性及脂质过氧化产物的影响,并观察肝脏组织的病理变化。与对照组相比,小鼠染毒后,血清中ALT、AST、DBIL和γ-GT明显升高;肝组织受到不同程度的损伤,HSI增大,蛋白质含量降低。当染毒剂量为1/4 LD₅₀时,肝脏中SOD活性和GSH-Px活性显著降低,MDA的含量则明显增加。实验结果表明,[C₁₄mim]Br可损伤小鼠的肝脏功能,破坏机体的抗氧化防御系统,造成氧化损伤和脂质过氧化。     

Organic Liquids Storage Tanks Volatile Organic Compounds (VOCS) Emissions Dispersion and Risk Assessment in Developing Countries: The Case of Dar-Es-Salaam City, Tanzania

The emission estimation of nine volatile organic compounds (VOCs) from eight organic liquids storage tanks companies in Dar-es-Salaam City Tanzania has been done by using US EPA standard regulatory storage tanks emission model (TANKS 4.9b). Total VOCs atmospheric emission has been established to be 853.20 metric tones/yr. It has been established further that petrol storage tanks contribute about 87% of total VOCs emitted, while tanks for other refined products and crude oil were emitting 10% and 3% of VOCs respectively. Of the eight sources (companies), the highest emission value from a single source was 233,222.94 kg/yr and the lowest single source emission value was 6881.87 kg/yr. The total VOCs emissions estimated for each of the eight sources were found to be higher than the standard level of 40,000 kg/yr per source for minor source according to US EPA except for two sources, which were emitting VOCs below the standard level. The annual emissions per single source for each of the VOCs were found to be below the US EPA emissions standard which is 2,000~kg/yr in all companies except the emission of hexane from company F1 which was slightly higher than the standard. The type of tanks used seems to significantly influence the emission rate. Vertical fixed roof tanks (VFRT) emit a lot more than externally floating roof tanks (EFRT) and internally floating roof tanks (IFRT). The use of IFRT and EFRT should be encouraged especially for storage of petrol which had highest atmospheric emission contribution. Model predicted atmospheric emissions are less than annual losses measured by companies in all the eight sources. It is possible that there are other routes for losses beside atmospheric emissions. It is therefore important that waste reduction efforts in these companies are directed not only to reducing atmospheric emissions, but also prevention of the spillage and leakage of stored liquid and curbing of the frequently reported illegal siphoning of stored products. Emission rates for benzene, toluene, and xylene were used as input to CALPUFF air dispersion model for the calculation of spatial downwind concentrations from area sources. By using global positioning system (GPS) and geographical information system (GIS) the spatial benzene concentration contributed by organic liquid storage tanks has been mapped for Dar-es-Salaam City. Highest concentrations for all the three toxic pollutants were observed at Kigamboni area, possibly because the area is located at the wind prevailing direction from the locations of the storage tanks. The model predicted concentrations downwind from the sources were below tolerable concentrations by WHO and US-OSHA. The highest 24 hrs averaging time benzene concentration was used for risk assessment in order to determine maximum carcinogenic risk amongst the population exposed at downwind. Established risk for adult and children at 2.9×10^-3 and 1.9×10^-3 respectively, are higher than the acceptable US-EPA risk of 1×10^-6. It is very likely that the actual VOCs concentrations in some urban areas in Tanzania including Dar-es-Salaam City are much higher than the levels reported in this study when other sources such as petrol stations and motor vehicles on the roads are considered. Tanzania Government therefore need to put in place: an air quality policy and legislation, establish air quality guidelines and acquire facilities which will enable the implementation of air quality monitoring and management programmes.     

两种咪唑氯盐类离子液体对水稻幼苗根部的毒性效应

按照毒性试验标准方法研究了1-癸基-3-甲基咪唑氯盐([DMIM]Cl)、1-十二烷基-3-甲基咪唑氯盐([C12MIM]Cl)对水稻幼苗生长的影响,测定了水稻根的半数抑制浓度(IC50-5d)、超氧化物歧化酶(SOD)活性、过氧化氢酶(CAT)活性、过氧化物酶(POD)活性、水稻根部丙二醛(MDA)含量及对水稻根系的生理影响.结果表明:两种离子液体(ILs)对水稻幼苗根部生长均具有抑制作用,随着浓度的增大抑制率增加,[DMIM]Cl和[C12MIM]Cl的根长IC50-5d分别为0.10 mg·L-1和0.054 mg·L-1,水稻幼苗根部对两种ILs均有氧化应激反应,在[DMIM]Cl和[C12MIM]Cl处理下,3种抗氧化酶活性均受到严重抑制,丙二醛(MDA)含量升高,加剧了水稻幼苗根部细胞膜脂质过氧化作用.[DMIM]Cl和[C12MIM]Cl处理导致根系活力降低,根系质膜透性增大.     

多元可燃混合溶液的闪点预测

为了预测多元可燃混合液的闪点,建立了一个预测模型,通过二元和三元可燃混合液闪点实测值的试验对比,证实此模型的误差在可接受的范围内。此模型可以在预知可燃混合液组分比例和单组分闪点基础上快速预测混合液的闪点。     

多孔介质中NAPLs流体毛细管指进形态及分形表征

非水相流体(non-aqueous phase liquids,NAPLs)如石油烃类和有机溶剂类污染土壤和地下水引起了广泛关注.不同粒径多孔介质中不同性质流体入渗形态的识别是确定污染范围、有效修复土壤和地下水的前提.本研究选取不同性质的4种NAPLs流体,建立可视化砂箱模型,比较4种流体在不同粒径石英砂中指流形态差异,并引入分形理论对迁移形态进行定量描述.结果表明,NAPLs流体指进过程属于毛细管指进,主要驱动力为毛细力;同种污染物或同一黏度数量级污染物之间指流宽度和渗流面积变化趋势与毛细管数和邦德数变化趋势呈负相关;指流宽度和渗流面积随着介质粒径的减小和流体黏度的增大而增加;指流宽度和渗流面积与渗流面的质量分形维数呈正相关,质量分形维数可以作为指流宽度和渗流面积的指示指标.