S(IV) Autoxidation in Atmospheric Liquid Water: The Role of Fe(II) and the Effect of Oxalate

The reactivity of dissolved iron compounds towards different pollutants and photooxidants in atmospheric liquid water depends upon the oxidation state and speciation of iron. Our measurements of the oxidation state of dissolved iron eluted from aerosol particles (Dae: 0.4–1.6 m) collected in the urban atmosphere of Ljubljana showed that a large fraction of the iron content is present as Fe(II). The concentration ratio [Fe(II)]/[Fe(III)] varied between 0.9 and 3.1. The kinetics of S(IV) autoxidation catalyzed by Fe(II) under the conditions representative for acidified atmospheric liquid water and the influence of oxalate on this reaction under dark conditions was investigated. The reaction rate is the same if Fe(II) or Fe(III) is used as a catalyst under the condition that Fe(II) can be oxidized in Fe(III), which is the catalytically active species. Oxalate has a strong inhibiting effect on the S(IV) autoxidation in the presence of Fe(II). The reaction is autocatalytic with an induction period, that increases with higher concentrations of oxalate. The inhibiting effect of oxalate differs according to whether iron is initially in the Fe(II) or Fe(III) state. However, in both cases the inhibition by oxalate is a result of the formation of complexes with the catalyst.     

自组织特征映射神经网络及其在彩色地图自动分层中的应用

地图数据分层是地图识别系统的一个重要组成部分。由于传统的基于Ｂａｙｅｓ准则识别方法要求已知概率分布密度，当实际概率分布与假设条件存在差异时，无法取得满意的识别效果。神经网络方法可以克服这些缺点。本文利用Ｋｏｈｏｎｅｎ提出的自组织特征映射网络的学习、识别能力，实现了对彩色地图扫描数据的自动分层。     

Degradation of Isoprene in the Presence of Sulphoxy Radical Anions

Autoxidation of S(IV) initiated by manganese sulphate or potassium peroxydisulphate in alkaline aqueous solutions was significantly slowed down by dissolved isoprene, which decayed in the process. The laboratory experiments were carried out in a batch, perfectly mixed reactor, which had no gas space. The concentration–time profiles of oxygen were measured with a Clark-type electrode. The profiles of sulphite species and of isoprene were evaluated from the UV spectra of solutions. The kinetic analysis indicated that isoprene reacted directly with sulphate radical anions produced during the S(IV) autoxidation. A relative second-order rate constant of (2.12 ± 0.37) × 10⁹ M^–1 s^–1 was determined for this reaction at 25 °C, pH (8.0–8.5) and ionic strength of (1.7–4.9) × 10^–3 M (the reference rate constant of the reaction of sulphate radical anions with sulphite ions equalled 3.4 × 10⁸ M^–1 s^–1). A tentative mechanism of isoprene oxidation during S(IV) autoxidation, which included formation of isoprene – SO^– ₄ adduct, was based on the analogy to the gas-phase reactions of isoprene and to the liquid-phase reactions of sulphate radical anions with other compounds. Atmospheric significance of the aqueous-phase reaction of isoprene with sulphate radicals was discussed. Approximate analysis showed the reaction is a potential sink for isoprene in the aqueous phase and in the gas–liquid systems of high liquid water content (LWC > 10^–5 m³ m^–3). The aqueous-phase oxidation of isoprene can produce secondary pollutants, and influence transformation and the long-range transport of SO₂ in the atmosphere.     

Inhibition of the S(IV) Autoxidation in the Atmosphere by Secondary Terpenic Compounds

To better understand the role of terpenic compounds in atmospheric chemistry the influence of sobrerol, a water-soluble product of photochemical autoxidation or ozonolysis of -pinene, on the rate of S(IV) autoxidation was studied. Laboratory experiments were performed under heterogeneous conditions, at constant supply with S(IV) by dissolution of CaSO₃.1/2 H₂O fine particles and with air oxygen by diffusion through a planar gas-liquid interface. The progress of S(IV) autoxidation, uncatalysed or catalysed by Fe₂(SO₄)₃ or CoSO₄, was followed conductometrically. The inhibiting effect of sobrerol was discussed in terms of the chain reaction terminated in a step linear with respect to sulphoxy radicals. A method was proposed for quantification of the inhibiting effect and the rate constant (2.0–3.8)10⁸ M^–1s^–1 was given for the step eliminating sulphate radicals. Further consequences of the inhibition: shifting the reaction locus from the gas-liquid (droplet) interface to the liquid (droplet) bulk and strong oscillations in the rate of S(IV) autoxidation resulting of the activity of sobrerol-derived radicals were also shown.     

硝酸根对颗粒状铁降解三氯乙烯的影响(英文)

为研究硝酸根对颗粒状铁降解三氯乙烯的影响,进行了柱实验和相应的反应铁腐蚀电位测定。在硝酸根离子存在条件下,铁的腐蚀电位相应升高,系统条件也因之发生变化,导致钝性的铁氧化物在铁表面生成。因而,三氯乙烯和硝酸根离子降解速率明显减小, 并且降解速率减小的程度与硝酸根离子的浓度成比例。当污染液流过反应柱时,硝酸根离子与铁反应, 被还原为氨根离子。该反应造成硝酸根离子的浓度梯度,使钝化区在柱中上移,从而影响了三氯乙烯的降解曲线。与三氯乙烯单独与铁反应相比,当含4 7 mg/L硝酸根的三氯乙烯溶液流经反应柱170 孔隙体积后,降解50% 三氯乙烯所需的时间(t50) 从小于4 h增加到大于10 h;而当三氯乙烯溶液中加入100 mg/L硝酸根离子,仅17 孔隙体积溶液流经反应柱后,三氯乙烯降解t50就已大于14 h。研究结果表明,由于硝酸根离子对铁的腐蚀电位和铁表面氧化膜的不利作用,在处理靶污染物为高浓度硝酸根离子和三氯乙烯共同污染的地下水时,铁渗透反应隔栅不是最佳选择。如果靶污染物中硝酸根离子浓度比较低,则在设计铁隔栅时应考虑到硝酸根离子造成的不利因素,相应增加铁墙的厚度,从而确保三氯乙烯的降解效果。     

Enzyme leach anomalies associated with deep Mississippi Valley-type zinc ore bodies at the Elmwood Mine, Tennessee

Deeply buried Mississippi Valley-type deposits that have been or are currently being mined in North America were initially discovered by drilling. Conventional geochemical methods are ineffective for detecting these ‘blind' deposits when they occur deep within sequences of stable-platform carbonates and shales. The ‘enzyme' leach is a selective analytical technique for determining trace elements associated with amorphous Mn oxide coatings in soils. In many areas of the world, the enzyme leach method is useful for detecting low-level geochemical anomalies in soils, which are associated with blind mineral deposits. Enzyme leach analysis of soils, collected at the Elmwood Mine, Tennessee, revealed high-contrast anomalies over ore bodies 370 m below the surface. In areas where the soils are in chemical equilibrium, ‘combination' anomalies occur over Zn ore bodies. These are characterized by asymmetrical halogen halos which occur around a halogen ‘central low'. Commodity metals (Zn and Pb) and trace elements associated with the ore (Cd, Ba, and Mn) form apical anomalies, which occur over the ore bodies and within the halogen halo. Under most circumstances, agricultural practices do not affect enzyme leach results. However, agricultural activity in central Tennessee appears to have altered the proportion of amorphous Mn oxides in the soils in some locations. Where the MnO₂-form equilibrium of the soil has been disturbed, enzyme leach data are erratic. In the one instance where this was encountered, ratioing the data to Mn reveals anomalies which bracket the blind ore bodies.     

共生生金菌与锰的相互作用机制

共生生金菌的生长具有周期性的变化特征，与锰相互作用也表现出了周期性的变化规律。该细菌影响着含锰溶液体系的ｐＨ和Ｅｈ，能将低价态的锰氧化为高价态的锰。细菌氧化锰主要借助于各种酶和不同代谢物的作用而完成。     

Precipitation of Fe and Al compounds from the acid mine waters in the dogyae area, Korea: A qualitative measure of equilibrium modeling applicability and neutralization capacity?

To investigate the applicability of equilibrium modeling for the estimation of the chemical changes of acid mine waters, the phases predicted to precipitate by equilibrium calculation were compared with what actually precipitates from the stream and acid mine waters in the Dogyae area, Korea. The computer program MINTEQA2 was used for the equilibrium calculations based on the chemical compositional data of the water samples collected in the study area. XRD, IR, thermal and chemical analyses of the collected precipitates were performed to identify their phases.The results of the identification of the collected precipitates are inconsistent with what the equilibrium calculations predict. The equilibrium calculations indicate that ferrihydrite, FeOHSO₄, gibbsite, and AlOHSO₄ should precipitate from the stream and acid mine waters in the study area. However, the experimental analyses show that only ferrihydrite and Al₄(OH)₁₀SO₄ are the recognizable precipitates on the bottom of the stream and mine drainage channels. Comparing the stability relations among the possible precipitates with the field occurrence of the precipitates in the study area suggests that FeOHSO₄ and AIOHSO₄ are kinetically inhibited to precipitate and metastable ferrihydrite and Al₄(OH)₁₀SO₄ appear in their stability field instead. It indicates that the chemical compositional change of the waters due to the solid phase precipitation in the study area must be interpreted and predicted in terms of the precipitation of not the phases predicted by the equilibrium calculation but the actually identified ones.Assuming that the dissolved species in the aqueous phase are in equilibrium with respect to the currently precipitating solid phases in the study area, the water chemistries are attempted to interpret based on the plot of the theoretically calculated activities of the dissolved species on the stability diagram for the identified precipitates and gibbsite. The plot reveals a few evolution paths of the chemical composition of the acid mine water as the acid generation and neutralization progress. The evolution path producing ferrihydrite and then Al₄(OH)₁₀SO₄ precipitation suggests that the system including acid producing pyrite has lost significant amounts of its neutralizing capacity and thus, become intolerable to the impacts from acid mine water.     

养护期介入电迁阻锈保障混凝土耐久性试验研究

沿海地区氯盐侵蚀会对混凝土结构造成严重的耐久性问题,混凝土设计使用寿命难以保障。对于新建工程,若在自由水含量较高混凝土养护期进行电迁阻锈处理,则有利于电迁移性阻锈剂在钢筋周围聚集以达到更佳的阻锈效果。为此,针对两种电迁移性阻锈剂对处于氯盐侵蚀环境中的混凝土适用性展开研究,并测试了干湿循环前后混凝土内钢筋电化学参数、氯离子扩散特征及钢筋周围电迁移性阻锈剂含量研究两种电迁移性阻锈剂对混凝土耐久性保障的作用。结果表明,试验中养护期介入电迁阻锈后试件阻锈效果良好,经过干湿循环后钢筋腐蚀电位正向高于-162.6 m V,同时,钢筋附近出现明显的阻锈剂聚集现象,能保持钢筋的钝化状态。