流动搅动法研究针铁矿对亚砷酸盐的吸附特征

采用流动搅动法,在溶液p H、浓度和温度影响条件下,研究针铁矿对亚砷酸盐吸附的特征.结果表明,在不同条件下,亚砷酸盐的吸附过程分为快反应和慢反应这2个阶段.随溶液p H的升高,砷的吸附量逐渐降低,表观吸附速率常数(k')逐渐增大,半反应时间(t1/2)也就越小,砷的吸附反应达到平衡时间就越短,且砷的扩散速率常数b值也逐渐降低.溶液p H 3.0和p H7.0时,砷最大吸附量分别为246.9 mg·kg~(-1)和99.8 mg·kg~(-1).随着砷浓度的升高,针铁矿对砷的吸附量增加,表观吸附速率常数(k')逐渐增大;砷浓度为0.10 mg·L~(-1)和1.00 mg·L~(-1)时,砷的最大吸附量分别为96.5 mg·kg~(-1)和249.1 mg·kg~(-1).Freundlich方程中吸附常数Kf值随着时间的延长逐渐降低,其吸附能力是逐渐减弱的.Langmuir方程分配因子RL在0~1之间,表现为针铁矿上砷的吸附为优惠吸附.随着温度的升高,针铁矿对砷的吸附量增加,表观吸附速率常数k'值也逐渐升高.温度为298K和313 K时,砷最大吸附量分别为241.1 mg·kg~(-1)和315.6 mg·kg~(-1).用抛物线扩散方程b值来计算扩散过程的伪热力学常数,砷吸附反应的活化能(E*a)为14.60 k J·mol~(-1).砷扩散活化焓变(ΔHθ)随着温度的升高有所降低,ΔHθ均为正值,扩散过程为吸热反应,升高温度有利于砷的吸附;活化自由能变(ΔGθ)随着温度的上升而升高,升高温度有利于加快扩散过程;ΔSθ值均为负,说明吸附反应使体系有序度增加.     

表面活性剂辅助离子液体预处理稻秆的酶解动力学与结构变化分析

以稻秆为原料进行酶解研究,考察了纤维素酶和β-葡萄糖苷酶单独作用及协同作用对稻秆酶解还原糖产量的影响,以确定最佳酶体系,并研究在最佳酶体系中不同种类表面活性剂辅助离子液体对稻秆酶解的影响和动力学特征,最后通过稻秆成分分析、FTIR、XRD、SEM对预处理前后的稻秆结构、结晶性进行了分析比较.结果表明,纤维素酶与β-葡萄糖苷酶具有协同作用,而且在最佳酶体系中,与未处理稻秆及单独离子液体预处理相比,不同种类表面活性剂辅助离子液体预处理的稻秆在酶水解48 h时纤维转化率分别增加40%~85%、10%~31%,并且预处理对反应速率的提高有促进作用.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.     

Variation of MCPA, metribuzine, methyltriazine-amine and glyphosate degradation, sorption, mineralization and leaching in different soil horizons

Pesticide mineralization and sorption were determined in 75 soil samples from 15 individually drilled holes through the vadose zone along a 28 km long transect of the Danish outwash plain. Mineralization of the phenoxyacetic acid herbicide MCPA was high both in topsoils and in most subsoils, while metribuzine and methyltriazine-amine was always low. Organic matter and soil pH was shown to be responsible for sorption of MCPA and metribuzine in the topsoils. The sorption of methyltriazine-amine in topsoil was positively correlated with clay and negatively correlated with the pH of the soil. Sorption of glyphosate was tested also high in the subsoils. One-dimensional MACRO modeling of the concentration of MCPA, metribuzine and methyltriazine-amine at 2 m depth calculated that the average concentration of MCPA and methyltriazine-amine in the groundwater was below the administrative limit of 0.1 μg/l in all tested profiles while metribuzine always exceeded the 0.1 μg/l threshold value.     

Photochemical behaviour of musk tibetene

BACKGROUND: Synthetic musk compounds are widely used as additives in personal care and household products. The photochemical degradation of musk tibetene in aqueous solutions or in acetonitrile/water mixtures under different conditions was studied in order to assess its environmental fate. METHODS: Musk tibetene dissolved (or suspended) in water and/or acetonitrile/water mixtures was irradiated at different times by UV-light and by solar light. The irradiation mixtures were analyzed by NMR and TLC. The photoproducts formed were identified by GC-MS and NMR data. RESULTS: The experimental results indicated that musk tibetene was photodegradable in water or acetonitrile/water mixtures with half-life reaction times close to 20 minutes. The irradiation mixtures were separated by chromatographic techniques yielding three photoproducts (3,3,5,6,7-pentamethyl-4-nitro-3H-indole, 3,3,5,6,7-pentamethyl-4-nitro-1H-indoline and 3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone) identified by means of spectroscopic analysis. DISCUSSION: The numerical modelling of the photodegradation concentration-time profiles gave (8.13 +/- 0.15) x 10(-2) and (1.34 +/- 0.04) x 10(-2) mol/E for the overall primary quantum yield of direct photolysis for musk tibetene and the major intermediate (3,3,5,6,7-pentamethyl-4-nitro-3H-indolinone), respectively, in the wavelength range 305-366 nm. The half-life times of photodegradation of the both substances varied from 1-1.5 hours at 20 degrees N during the summer season to 6-10 hours for highest latitudes in winter. CONCLUSIONS: Under solar light, musk tibetene was photolabile in acetonitrile and acetonitrile/water 1/1, while it was slowly degraded when suspended in water. In all media, musk tibetene was photodegraded into three photoproducts. By using a kinetic model, the overall primary quantum yields of direct photolysis of musk tibetene and its main photoproduct, in the wavelength range 305-366 nm, were estimated, indicating that the photodegradation rate for musk tibetene is faster than the photolysis rate of the major by-product. RECOMMENDATIONS AND PERSPECTIVES: The results indicate that, in order to assess the environmental impact of musk tibetene on the aquatic ecosystem, great attention should be focused on the major photoproduct which is proved to be more persistent than the parent compound under light irradiation. The predicted half-life times of direct photolysis for both substances ranged from 1-1.5 hours at 20 degrees N during the summer season to about 6-10 hours for highest latitudes in winter, indicating that, from a photochemical point of view, the environmental persistence of these substances increases by increasing the latitudes and during the cold seasons, making more realistic an intake of these xenobiotic molecules into the food chain of aquatic living organisms. Tanabe reports in his Editorial (Tanabe 2005) that "It is necessary to have knowledge of the global picture of synthetic musk pathways. So, it is conceivable that now is the time to study the transport, persistency, distribution, bioaccumulation and toxic potential of this new environmental menace on a global scale, especially in developing countries". Therefore, the future environmental analysis and investigations on the eco-toxicity of nitro musk compounds should take into account not only the presence of the parent compounds but also their photochemical intermediates or end-by-products.     

基于数字流域的水文过程模拟研究

考虑流域下垫面空间变异性,基于数字高程模型构建了数字流域,并在此基础上对描述流域水文物理过程的数学方法进行了探讨,文章认为,数字水文模型是一种有物理基础的包含大容量信息的现代模拟灌河实例研究表明,数字水文模型可以十分方便地输出水文要素和状态变量的空间分布与时间序列,这对充分利用现有观测信息进行水文信息的深层挖掘创新了条件。     

Extended geometric method: a simple approach to derive adsorption rate constants of Langmuir-Freundlich kinetics

A new and simple equation has been presented here for calculation of adsorption and desorption rate constants of Langmuir-Freundlich kinetic equation. The derivation of new equation is on the basis of extension and correction to the geometric method which has been presented by Kuan et al. [Kuan, W.-H., Lo, S.-L., Chang, C.M., Wang, M.K., 2000. A geometric approach to determine adsorption and desorption kinetic constants. Chemosphere 41, 1741-1747] for the kinetics of adsorption/desorption in aqueous solutions. The correction is to consider that the concentration of solute is not constant and changes as adsorption proceeds. The extension is that we applied Langmuir-Freundlich kinetic model instead of Langmuir kinetic model to consider the heterogeneity and therefore it is more applicable to the real systems. For solving Langmuir-Freundlich kinetic model, some geometric methods and also Taylor expansion were used and finally a simple and novel equation was derived (Eq. (20)) for calculation of adsorption rate constant. This new method was named "extended geometric method". The input data of the obtained equation can be simply derived from initial data of adsorption kinetics. Finally the adsorption of methyl orange onto granular activated carbon was carried out at dynamic and equilibrium conditions and the capabilities of extended geometric method were examined by the experimental data.     

土壤中4-溴苯胺降解动力学及其生态毒性追踪

秀谷隆是一种被广泛应用的取代脲类除草剂,其主要降解产物为４－溴苯胺（４－ＢＡ）,研究４－溴苯胺在不同土壤中的降解动力学规律,并用土壤环境指示动物弹尾目跳虫Ｃｏｌｌｅｍｂｏｌａ（Ｆｏｌｓｏｍｉａ ｃａｎｄｉｄａ）跟踪指示该化合物在进一步降解过程中的毒性,结果表明：４－溴苯胺在土壤中的降解行为可用一级反应动力学方程来较好地描述,其生态毒性明显高于母体化合物秀谷隆,该化合物在粘土中的残留量低于砂土,但毒     

谷氨酰胺转胺酶(MTG)分批发酵中温度对S.mobaraense生长及产酶影响的模型化

研究了2.5L小罐培养过程中控制温度为25℃～35℃时对细胞生长和MTG合成的影响.结果表明当控制相对较低的温度时,细胞生长的延滞期较长,当控制温度较高时,细胞生长的延滞期较短,达到最大DCW和最高MTG酶活的时间均较短;通过研究各种不同模型对细胞生长的影响得到最适合描述S.mobaraense生长与温度之间的关系方程为Schoolfield方程;通过对最大DCW和最大MTG酶活进行数学模拟,发现方程X(U)=-a     

Prognosis of the spatiotemporal dynamics of ecosystems by means of universal kriging

The use of quantitative data for constructing prognostic maps of the dynamics of ecosystem degradation and restoration by nonlinear simulation methods is a topical field of landscape ecology. This method of dynamic cartography is based on fiberwise comparison of data on the state of Chernye Zemli (the Kalmyk Republic, Russia) in different years and the detailed analysis of the period on which the prognosis was based. For this purpose, materials of repeated aerial and satellite photography obtained during a long period (1954–1993) were used. Comparison of maps characterizing the dynamics of Chernye Zemli between 1958 and 1993 allows prognostic electronic maps for the next 10–15 years (with a five-year interval) to be drawn and land prognosis for the next 20–30 years (1998–2023) to be obtained. Deceased