Experimentally determined dissolution kinetics of Na-rich borosilicate glass at far from equilibrium conditions: Implications for Transition State Theory     

Jonathan P. Icenhower  B. Peter McGrail  Eric M. Pierce  David K. Shuh  Jackie L. Steele 《Geochimica et cosmochimica acta》2008,72(12):2767-2788

The dissolution kinetics of five chemically complex and five chemically simple sodium silicate glass compositions (Na-Si±Al±B) were determined over a range of solution saturation values by varying the flow-through rates (1-100 mL/d) in a dynamic single-pass flow-through (SPFT) apparatus. The chemically complex borosilicate glasses are representative of prospective hosts for radioactive waste disposal and are characterized by relatively high molar Si/(Si + Al) and Na/(Al + B) ratios (>0.7 and >1.0, respectively). Analysis by X-ray absorption spectroscopy (XAS) indicates that the fraction of ^ivB to ⁱⁱⁱB (N₄) varies from 0.66 to 0.70. Despite large differences in bulk chemistry, values of δ²⁹Si peak shift determined by MAS-NMR varies only by about 7 ppm (δ²⁹Si = −94 to −87 ppm), indicating small differences in polymerization state for the glasses. Forward rates of reaction measured in dynamic experiments converge (average log₁₀ rate [40 °C, pH 9] = −1.87 ± 0.79 [g/(m² d)]) at high values of flow-rate (q) to sample surface area (S). Dissolution rates are independent of total Free Energy of Hydration (FEH) and this model appears to overestimate the impact of excess Na on chemical durability. For borosilicate glass compositions in which molar Na > Al + B, further addition of Na appears to stabilize the glass structure with respect to hydrolysis and dissolution. Compared to other borosilicate and aluminosilicate glasses, the glass specimens from this study dissolve at nearly the same rate (0-∼56×) as the more polymerized glasses, such as vitreous reedmergnerite (NaBSi₃O₈), albite, and silica. Dissolution of glass follows the order: boroaluminosilicate glass > vitreous reedmergnerite > vitreous albite > silica glass, which is roughly the same order of increasingly negative ²⁹Si chemical shifts. The chemical shift of ²⁹Si is a measure of the extent of bond overlap between Si and O and correlates with the forward rate of reaction. Thus, dissolution appears to be rate-limited by rupture of the Si-O bond, which is consistent with the tenants of Transition State Theory (TST). Therefore, dissolution at far from equilibrium conditions is dependent upon the speed of the rate-controlling elementary reaction and not on the sum of the free energies of hydration of the constituents of boroaluminosilicate glass.  相似文献   

大别山北部黄土岭片麻岩的锆石U-Pb年龄和氧同位素组成：古老的原岩和多阶段历史   总被引：6，自引：0，他引：6  

夏群科郑永飞  葛宁洁EtienneDELOULE 《岩石学报》2003,19(3):506-512

利用阴极发光和离子探针技术，对大别山北部黄土岭片麻岩的锆石进行了内部结构、U-Pb年龄和氧同位素组成的系统分析。黄土岭片麻岩的锆石具有核-幔-边三层结构，核部是原岩的岩浆锆石，形成时代为-2800Ma；幔部是变质重结晶的产物，变质作用的时代为-2000Ma；边部则是在-110Ma从部分熔融体里结晶出来的增生锆石，是受大别山燕山期构造-岩浆事件影响的反映。黄土岭片麻岩和麻粒岩中-2800Ma和-2000Ma的年龄，以及麻粒岩中约3400Ma的残留锆石年龄均可以与扬子崆岭群变质岩对比。由此可以推断，北大别在构造属性上属于扬子板决，扬子与华北板决的缝合线应在北大别以北。锆石的核-幔-边具有不同的氧同位素组成，氧同位素数据表明黄土岭片麻岩的原岩是S型花岗岩，在-2000Ma和-110Ma的事件中都有外来物质(流体或熔体)的加入。  相似文献   

Dissolution of Columbia River Basalt under mildly acidic conditions as a function of temperature: Experimental results relevant to the geological sequestration of carbon dioxide     

H. Todd Schaef  B. Peter McGrail 《Applied Geochemistry》2009

Increasing attention is being focused on the rapid rise of CO₂ levels in the atmosphere, which many believe to be the major contributing factor to global climate change. Sequestering CO₂ in deep geological formations has been proposed as a long-term solution to help stabilize CO₂ levels. However, before such technology can be developed and implemented, a basic understanding of H₂O–CO₂ systems and the chemical interactions of these fluids with the host formation must be obtained. Important issues concerning mineral stability, reaction rates, and carbonate formation are all controlled or at least significantly impacted by the kinetics of rock–water reactions in mildly acidic, CO₂-saturated solutions. Basalt has recently been identified as a potentially important host formation for geological sequestration. Dissolution kinetics of the Columbia River Basalt (CRB) were measured for a range of temperatures (25–90 °C) under mildly acidic to neutral pH conditions using the single-pass flow-through test method. Under anaerobic conditions, the normalized dissolution rates for CRB decrease with increasing pH (3 ? pH ? 7) with a slope, η, of −0.15 ± 0.01. Activation energy, E_a, has been estimated at 32.0 ± 2.4 kJ mol⁻¹. Dissolution kinetics measurements like these are essential for modeling the rate at which CO₂-saturated fluids react with basalt and ultimately drive conversion rates to carbonate minerals in situ.  相似文献   

Hydrogen Isotopic Compositions of Pyroxenes in Nushan Peridotite Xenoliths,SE China     

YU Huimin  XIA Qunke  E.DELOULE  YANG Xiaozhi CAS Key Laboratory of Crust-Mantle Materials  Environments  School of Earth  Space Sciences  University of Science  Technology of Chin  Hefei  Anhui  Chin  CRPG-CNRS  BP  Vandoeuvre Cedex  France 《《地质学报》英文版》2005,79(3):336-342

Hydrogen isotopic compositions of pyroxenes in peridotite xenohths from the Nushan volcano, Anhui Province, SE China have been obtained using an ion probe (Cameca 1270). D/H ratios are constant within a single grain and among the different grains from the same sample. The lack of correlation between the D/H ratios and the hydrogen contents indicates that the hydrogen isotopic compositions are inherited from their mantle source. Combining with the δD values of coexisting amphiboles, it is inferred that the Nushan mantle experienced at least a two-stage metasomatic event.One was responsible for formation of amphiboles with extremely variable δD values, and the other was probably responsible for the high δD values (up to -20‰) of some clinopyroxenes from peridotites, clinopyroxene and mica megacrysts. High δD values point to a subduction-related fluid being involved in one metasomatic event. The primary δD values (-90‰ to -140‰) of the Nushan pyroxenes, together with data gleaned from the literature, suggest that the D/H ratios of the nominally anhydrous mineral reservoir might have differed from that of the other mantle hydrogen in being relatively depleted in D.  相似文献