Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

Brønsted reactions on oxide mineral surfaces and the temperature-dependence of their dissolution rates

The pH-dependence of oxide dissolution rates is controlled by Brønsted acid-base reactions at the mineral surface. These reactions are rapid but depend explicitly on temperature, as do the subsequent slow rates of bond hydrolysis. The net result is that dissolution rates vary in a complicated fashion with temperature and solution pH. The enthalpy changes of acid-base reactions on oxide materials are sufficiently similar, however, that general statements can be made about their contribution. The enthalpy changes from proton adsorption to a hydroxyl functional group (SOH), or to a deprotonated functional group (SO ^–), are generally exothermic. The enthalpy changes become increasingly endothermic, however, as charge accumulates on the mineral surface and the charged species interact electrostatically. The result is that mineral dissolution rates are least sensitive to temperature, as measured with an Arrhenius-like rate law, at pH conditions near the Point of Zero Net Proton Charge.     

Nature minéralogique et rôle nutritionnel des argiles de sols céréaliers en région subhumide à semi-aride (Tunisie)

The cereal soils of the Northwest of Tunisia derive most of the time, from alluvial deposits or altered remains of carbonated and clayey rocks. Extraction of the clayey fraction permitted to reveal the presence of the following clayey minerals: kaolinite, illite, smectite, chlorite, as well as an illite–smectite interstratified layer, which is present in the deep horizons of the vertisol and in the isohumic soil. The presence of such types of clays shows that the evolution mechanism of soils is weathering of primary minerals inherited from the sedimentary rocks of the Northwest of Tunisia. These clays ensure to soils most of their cationic exchange capacity. Thanks to these clays, which have Ca⁺⁺, Mg⁺⁺ and K⁺ as exchangeable cations, the chemical fertility of these soils is ensured. It may be improved by increasing contents of organic matter, which is naturally few abundant in these soils. To cite this article: H. Ben Hassine, C. R. Geoscience 338 (2006).     

25～75℃酸性NaCl溶液中方铅矿的溶解动力学

在25～75℃、pH=0.43～2.45的1mol/LNaCl溶液中进行了方铅矿的溶解动力学实验。发现在远平衡条件下,方铅矿的溶解速率r与氢离子活度犤H+犦呈线性关系,溶解速率方程(速率定律)为:r=k犤H+犦,即对H+而言,溶解反应为一级。其中速率常数k为2.344×10-7mol/m2·s(25℃)、1.380×10-6mol/m2·s(50℃)、7.079×10-6mol/m2·s(75℃)。溶解反应的活化能为43.54kJ/mol,方铅矿的溶解机理为表面化学反应,速率决定步骤为表面配合物的离解。     

MODELING THE FATE AND TRANSPORT OF HYDROPHOBIC ORGANIC COMPOUNDS IN AN UNSTEADY RIVER-ESTUARINE SYSTEM

1 INTRODUCTION Extensive literature (Brown et al., 1985; Sawhney et al., 1981; Bierman and Swain, 1982; Connolly, 1980; Lopez-Avila and Hites, 1980; O扖onnor, 1988) described lots of sorbed pollutants or toxic substances in bed sediments of rivers, even after the effluent was halted for a long time. This is particularly true for hydrophobic organic compounds that can be sorbed on the particles and accumulated in the river bed sediments (Karickhoff et al., 1979). Pollution events of…     

In situ methods for studying adsorbed phases at the solid/liquid interface: microcalorimetry and ellipsometryLes méthodes d'étude in situ des phases adsorbées : microcalorimétrie et ellipsométrie

The applications of calorimetric and ellipsometric methods to the understanding of adsorption phenomena occurring at the solid–liquid interface are presented with examples in the field of surfactant adsorption. The various experimental approaches are presented and compared, i.e., immersion calorimetry, titration calorimetry and liquid flow calorimetry. It is shown how they can be used to follow, in situ, the building steps of the surfactant adsorbed layer. On the other hand, ellipsometry allows the adsorption isotherm, the adsorption kinetics as well as the thickness of the adsorbed layer to be determined on well-defined flat surfaces. To cite this article: R. Denoyel, C. R. Geoscience 334 (2002) 689–702.     

湍流混合动力学机理研究

在分析传统混合动力学机理基础上,通过宏观混合与微观混合时间量级的对比,提出了湍流条件下,涡流扩散主导宏观混合,分子扩散主导微观混合,而混合过程由宏观混合主导,欧拉数Eu可作为混合效果的控制指标,并通过3种不同容积反应器的混合搅拌试验,进一步证实了该指标的实用性。     

Kinetics of Disproportionation of Inorganic Polysulfides in Undersaturated Aqueous Solutions at Environmentally Relevant Conditions

The rate of the reversible homogeneous disproportionation of polysulfides was studied by following the optical absorbance of polysulfide solutions in a continuous plug flow reactor equipped with an on-line photometric detector. In order to avoid heterogeneous slow reactions involving sulfur colloids or precipitate, the reaction was initiated by an abrupt pH change from an undersaturated solution containing predominantly tetrasulfide species to a pH where pentasulfide is the dominant species. The disproportionation was found to follow first order reversible reaction dynamics. At environmentally relevant conditions the characteristic time of the disproportionation reaction is of the order of 10 s. This characteristic time implies that necessary conditions for speciation of the different polysulfide species by chromatography or another separation and subsequent quantification scheme should be of the order of 1 s.     

环电流区中性原子观测特性模拟研究

为了给双星计划中性原子(ENA)探测仪的研制提供可靠 的理论依据，并为未来中性原子探测数据的分析及研究做好准备，针对双星轨道初步模拟计 算了双星ENA探测仪对磁暴时中性原子的观测特性. 建立了磁暴主相期间环电流离子分布的 一 个近似理论模式，并模拟计算了极轨卫星在极区上空、赤道面以及其他位置上对不同强度磁 暴主相期间环电流区ENA空间角分布及能谱的观测结果. 研究表明，存在环电流区方向和南 北极区环电流粒子沉降带两个中性原子强度极大区域；磁暴越强烈，注入区高度越低，环电 流区观测到的ENA通量越高；处于有利位置的ENA探测器可分辨注入区内边界或注入前沿；EN A探测器能够分辨环电流带离子分布的不均匀性；由于离子交换截面的差异，H，O，He 3种E NA的能谱分布不同；在10～80keV能谱范围内通量较强，易于观测；环电流区H，O两种ENA 通 量较强，有利于观测；而环电流区He ENA通量很弱，不易于观测. 模拟计算研究表明，双星 极轨卫星能够对环电流区ENA进行有效探测；低纬轨道上的ENA探测器也能够对环电流区ENA 进行一些观测；ENA探测器的研制应重视低、中能量范围ENA的探测.