Asymmetrically zoned reaction rims: assessment of grain boundary diffusivities and growth rates related to natural diffusion-controlled mineral reactions

This study explores garnet coronas around hedenbergite, which were formed by the reaction plagioclase + hedenbergite→garnet + quartz, to derive information about diffusion paths that allowed for material redistribution during reaction progress. Whereas quartz forms disconnected single grains along the garnet/hedenbergite boundaries, garnet forms ～20‐μm‐wide continuous polycrystalline rims along former plagioclase/hedenbergite phase boundaries. Individual garnet crystals are separated by low‐angle grain boundaries, which commonly form a direct link between the reaction interfaces of the plagioclase|garnet|hedenbergite succession. Compositional variations in garnet involve: (i) an overall asymmetric compositional zoning in Ca, Fe²⁺, Fe³⁺ and Al across the garnet layer; and (ii) micron‐scale compositional variations in the near‐grain boundary regions and along plagioclase/garnet phase boundaries. These compositional variations formed during garnet rim growth. Thereby, transfer of the chemical components occurred by a combination of fast‐path diffusion along grain boundaries within the garnet rim, slow diffusion through the interior of the garnet grains, and by fast diffusion along the garnet/plagioclase and the garnet/hedenbergite phase boundaries. Numerical simulation indicates that diffusion of Ca, Al and Fe²⁺ occurred about three to four, four and six to seven orders of magnitude faster along the grain boundaries than through the interior of the garnet grains. Fast‐path diffusion along grain boundaries contributed substantially to the bulk material transfer across the growing garnet rim. Despite the contribution of fast‐path diffusion, bulk diffusion through the garnet rim was too slow to allow for chemical equilibration of the phases involved in garnet rim formation even on a micrometre scale. Based on published garnet volume diffusion data the growth interval of a 20‐μm‐wide garnet rim is estimated at ～10³–10⁴ years at the inferred reaction conditions of 760 ± 50 °C at 7.6 kbar. Using the same parameterization of the growth law, 100‐μm‐ and 1‐mm‐thick garnet rims would grow within 10⁵–10⁶ and 10⁶–10⁷ years respectively.     

Carbonyl products of the gas phase reaction of ozone with 1,1-disubstituted alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃+R₁R₂C=CH₂ (HCHO+R₁R₂COO)+(1–)(R₁COR₂+H₂COO) where formaldehyde and the ketone R₁ COR₂ are the primary carbonyls and R₁R₂COO and H₂COO are the corresponding biradicals. Measured values of were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H₂COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R₁R₂COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.     

Seasonal and Diurnal Variation of Surface Ozone and a Preliminary Analysis of Exceedance of its Critical Levels at a Semi-arid Site in India

The mixing ratios of surface O₃ were measured at St. John's College, Agra, an urban and traffic influenced area for the period of 2000–2002. The monthly averaged O₃ mixing ratios ranged between 8 to 40 ppb with an annual average of 21 ppb. Strong diurnal and seasonal variations in O₃ mixing ratios were observed throughout the year except for monsoon season. The mixing ratios of O₃ follow the surface temperature cycle and solar radiation (r = 0.72 and r = 0.65 with temperature and solar radiation, respectively). Concentrations were higher with winds associated with NE and NW direction indicating the impact of pollution sources on surface O₃ concentration. Exceedance of ozone critical level was calculated using the AOT 40 index and found to be 840 ppb.h and 2430 ppb.h for summer and winter seasons, respectively. The present O₃ exposures are lower than the critical level of O₃ and suggest that the present level of O₃ does not have any impact on reduction in crop yields.     

载荷试验确定基床系数修正方法的讨论

Winkler地基模型是目前工程界应用最广的一种地基模型，但对其关键参数——基床系数k的确定，许多文献的表述并不一致。该文在大量试验资料的基础上，通过对该问题的深入研究，阐明了通过载荷试验确定基床系数修正方法的有关概念。对于砂性土地基，载荷板试验得出的基准基床系数仅需要进行基础大小修正，而对于粘性土地基，则需要进行基础大小和基础形状两项修正。     

地浸采铀浸出液氧化沉淀法除铁研究

在氧化沉淀法去除铁的过程中,氧化反应分别在自然曝气、充气和除钙的条件下进行,对照结果进行分析,得出最佳的除铁配方,同时还着重对氧化反应速率及其影响因素（pH,Eh等）进行了探索性研究,为以后试验提供了一定的依据。     

凹凸棒石与Zn^2＋的长期作用研究

以凹凸棒石与Zn2＋为例研究粘土矿物与重金属离子长期作用过程,并运用高分辨透射电镜和X射线衍射分析粘土矿物与重金属离子长期作用的次生物相。结果表明：Zn2＋与凹凸棒石的长期作用是一个二阶段的过程,初始阶段为快速吸附作用,其后表现为慢速沉淀反应。高分辨透射电镜和X射线衍射分析表明,凹凸棒石与Zn2＋的长期作用过程中,具有纳米矿物特性的凹凸棒石表面快速水化,提高了悬浮液的pH值,诱导Zn2＋水解沉淀。而后,凹凸棒石缓慢溶解释放Al3＋和SiO44-与Zn（OH）2沉淀反应,形成Zn-A1双氢氧化物和异极矿。这一结果对认识土壤环境中重金属与粘土矿物的作用及重金属的归宿具有重要意义。     

锰矿石脱硫产物处理含铜废水动态实验研究

氧化型锰矿石脱硫产物含大量硫化锰,利用这种材料装填固定床进行净化水中铜离子的动态试验.在材料粒径0.45～0.9mm、进水pH=5.8、进水滤速4.58 m/h条件下,1 t锰矿石脱硫产物可以处理923 tρ(Cu~(2+))=50 mg/L的含铜废水,出水ρ(Cu~(2+))<0.5 mg/L,低于国家一级排放标准.控制进水pH在4～9之间、降低进水滤速、采用较小粒径的材料有利于提高锰矿石脱硫产物处理含铜废水的容量.利用X射线粉末衍射(XRD)和扫描电镜-能谱分析(SEM-EDS)对材料和产物进行表征,证明锰矿石脱硫产物去除水中铜离子是基于离子交换反应的原理.     

Climatology of Ozone, PAN, CO, and NMHC in the Free Troposphere Over the Southern North Atlantic

Free tropospheric measurements of ozone, peroxyacetylnitrate andprecursors (CO, NMHC) that were made within the framework of the EUROTRACsub-project TOR (Tropospheric Ozone Research) between 1990 and 1995 at theGAW station Izana, Tenerife (28°18N, 16°30W) arediscussed. The average annual cycles reveal the importance of transport fromnorthern mid-latitudes and the role of photo-chemistry. According toair-mass trajectories, which were supplied to us from AEROCE(Atmosphere/Ocean Chemistry Experiment), transport from northernmid-latitudes is associated with high precursor concentrations in winter,whereas ozone concentrations in winter are not much influenced by transportpatterns, suggesting a rather uniform distribution over the northern part ofthe Northern Hemisphere around mean value of 43 ± 5 ppb. In summer,high ozone concentrations of up to 90 ppb are often encountered duringtransport from north, while the levels of precursors are much lower than inwinter, because of photochemical destruction. Trajectories from southerlylatitudes and the Sahara usually have the lowest ozone concentrationsassociated with them.     

Predicting size effect on diffusion-limited current density of oxygen reduction by copper wire

The size effect of copper wire radius (0.04–0.82 mm) on the diffusion-limited current density of an oxygen reduction reaction in stagnant simulated seawater (naturally aerated 0.5 mol/L NaCl) is investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) and compared with the results obtained in 0.5 mol/L H2SO4. In the oxygen diffusion-limited range, size effect is found to occur independent of electrolytes, which is attributed to non-linear diffusion. Additionally, to sati...