Low-temperature thermodynamic model for the system Na2CO3−MgCO3−CaCO3−H2O

A comprehensive low-temperature thermodynamic model for the geochemically important Na₂CO₃−MgCO₃−CaCO₃−H₂O system is presented. The model is based on calorimetrically determined Δ_fH°₂₉₈ values, S°₂₉₈ values and C°_p(T) functions taken from the literature as well as on μ°₂₉₈ values of solids derived in this work from solubility measurements obtained in our laboratories or by others. When these thermodynamic quantities were combined with temperature-dependent Pitzer parameters taken from the literature, solubilities calculated for a wide range of conditions agree well with experimental data. The results for several subsystems were summarized by depicting the respective phase diagrams. For the MgO−CO₂−H₂O subsystem, it was found that the commonly believed stability relations must be revised, i.e., in the temperature range covered, nesquehonite never becomes more stable than hydromagnesite at p_CO2 ≤ 1 atm. Although the recommended set of thermodynamic data on sparingly soluble solids was derived from experimental results on mainly NaClO₄ systems, it can be incorporated in databanks containing additional Pitzer parameters for modeling more complex fresh- or seawater systems.     

Cordierite-garnet-sillimanite-quartz equilibrium: I. New experimental calibration in the system FeO−Al2O3−SiO2−H2O and certain P-T-X H2O relations

The equilibrium in which hydrous Fe-cordierite breaks down to almandine, sillimanite, quartz, and water was previously experimentally determined by Richardson (1968) and Holdaway and Lee (1977) using QMF buffer and by Weisbrod (1973) using QIF buffer. All these studies yielded similar results — a negative dP/dT slope for the equilibrium curve. However, based on theoretical arguments, Martignole and Sisi (1981), and based on Fe-Mg partitioning experiments on coexisting cordierite and garnet in equilibrium with sillimanite and quartz, Aranovich and Podlesskii (1983) suggested that this equilibrium curve has a positive dP/dT slope and its position depends on the water content of the equilibrium cordierite. We have redetermined this equilibrium using a much improved tecnique of detecting reaction direction, and cordierite starting material that contained virtually no hercynite. Hercynite was present as a contaminant in the cordierites of previous experimental studies and possibly reacted with quartz during the experimental runs to expand the apparent stability field of Fe-cordierite. We synthesized Fe-cordierite from reagent grade oxides at 710°C and 2 kbar (using QMF buffer) with two intermediate stages of grinding and mixing. The cordierite has a unit cell volume of 1574.60 ų (molar volume=23.706 J/bar) and no Fe³⁺ as indicated by X-ray diffraction and room temperature Mössbauer studies respectively. Reaction direction was concluded by noting20% change of the ratios of intensities of two key X-ray diffraction peaks of cordierite and almandine. Our results show that the four-phase equilibrium curve passes through the points 2.1 kbar, 650°C and 2.5 kbar, 750°C. This disagrees with all previous experimental studies. H₂O in the Fe-cordierite, equilibrated at 2.2 kbar and 700°C and determined by H-extraction line in the stable isotope laboratory, is 1.13 wt% (n=0.41 moles). H₂O content of pure Mg-cordierite equilibrated under identical conditions and determined by thermogravimentric conditions and determined by thermogravimetric analysis is 1.22 wt% (n=0.40). Similar determinations on Fe-cordierite and Mg-cordierite equilibrated at 2.0 kbar and 650°C show 1.27 wt% (n=0.46) and 1.47 wt% (n=0.48) of H₂O respectively. Thus, H₂O content appears to be independent of Fe/Mg ratio in cordierite, a conclusion which supports previous experimental determinations. The experimentally determined equilibrium curve represents conditions of P_H2O=P_total. From this we calculated the anhydrous curve representing equilibrium under conditions of X _H2O ^V =0.0. A family of calculated equilibrium curves of constant n _H2O ^Cord cut the experimentally determined curve at a very small angle indicating a slight variation in n _H2O ^Cord in cordierite in equilibrium with almandine, sillimanite, and quartz under the conditions of constant X _H2O ^V . Ancther set of calculated equilibrium curves, each representing constant a _H2O ^V demonstrate that the slopes of the curves vary with X _H2O ^V , and are all positive in the full range of 0.0X _H2O ^V 1.0.     

土−桩基−隔震支座−核岛地震反应试验研究

通过开展大型地震模拟振动台试验,对比研究了土−桩基−隔震支座−核岛结构和土−桩基−核岛结构的地震反应。试验采用橡胶铅锌支座作为基础隔震,放置于桩基承台和上部核岛结构之间,地基土采用某工程场地的均匀粉质黏土,试验输入的地震动时程,是由美国核电设计的 RG1.60 反应谱拟合而成。试验结果表明：隔震支座不仅可以改变上部结构频率、减小加速度和反应谱幅值大小,还可以减少下部桩的弯矩,起到降低上部结构的反应的隔震作用。但隔震支座的使用会改变桩基础的弯矩分布,核电工程采用隔震支座时应对桩基受力和变形进行特殊抗震设计,以保证土−桩−上部结构整体系统的抗震稳定性。     

An optical transform and Monte Carlo study of the diffuse X-ray scattering in mullite,Al2(Al2+2xSi2−2x)O10−x

Diffuse X-ray scattering distributions have been recorded for reciprocal layers normal to c ^* of a synthetic mullite with composition Al₂(Al_2+2xSi_2–2x) O_10–xx, where represents an oxygen vacancy and x is close to 0.4. The effect on the diffuse scattering pattern of different schemes for ordering of the oxygen vacancies and the accompanying cation shifts within a single ab-layer of mullite has been investigated using optical diffraction analogue experiments in conjunction with Monte Carlo simulation.A simple scheme in which the only driving force for the ordering is that the O_c oxygens are precluded from being bonded to four T/T^* cations, results in a 2D diffuse intensity distribution which displays many of the features that are observed in the x-ray scattering patterns. An alternative scheme in which bonding to four T/T^* cations was favoured, resulted in a domain structure consisting of islands of the -alumina structure within a matrix of sillimanite. This gave diffraction patterns bearing no resemblance to the observed x-ray patterns and can, we believe, be discounted completely.     

EPR investigation of NO2 and CO2 − and other radicals in beryl

A number of different impurities are located in the open channels of natural beryl crystals. The rare Maxixe beryl contains an unusual amount of NO₂. The isoelectronic CO₂ ⁻ radical is found in the irradiated Maxixe-type beryl. The NO₂ radicals are distributed in the Be–Al plane of the crystal, with the nitrogen atom close to the oxygens of the beryl cavity wall. These oxygens repel the negative CO₂ ⁻ radical, which is located at the center of the beryl cavity and rotates around its O–O axis, which is parallel to the crystal c-axis. When there is a nearby alkali ion at the center of the beryl channel, it reorients the CO₂ ⁻ radical so that its bisector is parallel to the c-axis and points toward the positive ion. Different signals are analyzed for Li⁺, Na⁺, and another counter-ion, which probably is Cs⁺. The related NO₃ and CO₃ ⁻ radicals are the color centers in the investigated deep blue beryls. The slow decay of the color, which makes these beryls useless as gem stones, is related to the decay of the hydrogen atoms which are present in these crystals. Evidence is given that NO₃ is created in Maxixe beryl by a natural process, while CO₃ ⁻ in Maxixe-type beryl has been created by irradiation. The temperature dependence of the EPR signals of these two radicals was investigated, but a definitive proof that they rotate at the center of the beryl cavity could not be given. EPR signals from some other radicals in beryl have been observed and described.     

Nitrate removal from water using UV-M/S2O4 2− advanced reduction process

In this work, a new process called advanced reduction process (ARP) was used for nitrate removal from water. This ARP process combines sodium dithionite as reducing agent with ultraviolet irradiation using medium pressure lamps (UV-M) as an activating method. Experimental results showed that UV-M/S₂O₄ ^2? process achieved almost complete removal of nitrate from aqueous solutions containing 25 mg NO₃ ^?/L using stoichiometric dose of dithionite of 68.8 mg/L at neutral pH conditions. Analysis of final products and material balance confirmed that NO₃ ^? ions were reduced to ammonium with formation of nitrite as intermediates in addition to the formation of small amounts of volatile species, mainly ammonia and nitrogen gas. Effects of certain experimental parameters including dithionite dose, initial pH, initial nitrate concentration, and UV light source on the kinetics and efficiency of nitrate reduction were evaluated. Increasing dithionite dose augmented the rate of nitrate reduction and enhanced the efficiency of ARP process. Dithionite doses higher than stoichiometric ratios led to complete removal of nitrate in shorter reaction time. UV-M/S₂O₄ ^2? process was found to be effective only under neutral pH or alkaline conditions, and its removal efficiency is negligible in acidic medium (pH < 4). Irradiation with UV-M was more effective than low pressure or narrow band lamps. These results can be attributed to the contribution of several mechanisms for nitrate reduction to ammonium. These include the following: direct photolysis, chemical reduction of nitrate dithionite, and mediated reduction of nitrate by free reducing radicals.     

絮凝−真空−电渗联合加固滩涂软土的模型试验研究

针对真空预压作用下排水板淤堵与排水条件受限等问题,提出絮凝−真空−电渗联合加固法。首先通过沉降柱试验确定合适的有机絮凝剂,然后采用该絮凝剂,分别在 48 h（开始介入真空预压,固结度为0 ）、60 h（排水速率明显下降,固结度为60%）及 84 h（排水速率近乎 0,固结度为 80%）时介入电渗,开展不同电渗介入时间的絮凝−真空−电渗联合加固试验。试验从排水量、十字板剪切强度、含水率与孔压等对比分析联合加固的有效性,确定其最佳电渗介入时间。试验结果表明：当固结度为 80% 时介入电渗,絮凝−真空−电渗联合加固法能够有效地抑制排水速率减小的趋势,增长有效排水时间。同时,土体的抗剪强度和承载力亦得到大幅提升,孔压消散更加均匀。此外,在阳离子聚丙烯酰胺絮凝剂的作用下,初始排水速率快,在一定程度上使土体的渗透性得到提升,有效地解决了排水板淤堵问题,说明絮凝−真空−电渗联合加固法具有较强的优越性。     

热−水−力耦合条件下黏土岩蠕变特性研究

黏土岩作为放射性核废料处置的备选介质,长期处于热-水-力耦合的复杂条件下。为研究围岩的长期稳定性,开展了一系列不同围压和偏应力下的黏土岩加温-降温排水蠕变试验。得出以下结论：温度的升高会提升黏土岩的蠕变速率,延长衰减蠕变阶段的时间,但是降温过程中试样主要以冷缩变形为主,并未见明显的蠕变变形;围压的降低以及偏应力的增加会提高黏土岩的蠕变速率,并且这种影响会随温度的升高明显加剧。基于试验结果,在Perzyna过应力理论的基础上引入蠕变硬化、蠕变损伤以及热损伤,建立了黏土岩热-水-力耦合蠕变模型。通过ABAQUS软件及其子程序对该模型进行数值实现,模拟结果与试验结果的对比初步表明该模型可以很好地描述热-水-力耦合条件下黏土岩的蠕变特性。     

非饱和土中热−湿−盐耦合作用的稳态分析

以多孔介质理论为基础,研究了稳态条件下非饱和土中温度?水分?盐分多场耦合问题。考虑非饱和土的孔隙被液态水、溶解的盐分、水蒸气和干燥气体等填充,在质量和能量守恒的基础上获得了非饱和土中水分、气体、盐分的质量守恒方程以及能量守恒方程。考虑一维稳态问题,选取温度、孔隙气压、孔隙水压和盐溶液浓度以及它们的导数作为状态变量,得到了问题的状态方程组。在给定的边界条件下,采用打靶法求解了该强耦合的非线性变系数微分方程组,通过与已有的试验结果相比较,验证了模型的有效性。基于数值算例,参数分析了含水率、温度边界、孔隙率等条件对非饱和土中温度场、水分场和盐分场分布的影响规律。     

强震区桩−土−断层耦合作用下桩基动力响应

为研究桩-土-断层耦合作用下桩基动力响应特性,利用振动台试验选取0.35g地震动峰值加速度时4种类型地震波,研究断层上下盘桩基加速度响应、桩顶相对位移、弯矩及桩基损伤情况。试验表明：断层上盘桩基各项参数明显大于断层下盘,呈现出上盘效应;桩顶峰值加速度大于桩底峰值加速度,上部土层对输入地震波具有滤波作用;桩顶加速度响应相较于桩底具有滞后性;桩顶峰值加速度与桩顶加速度放大系数α在输入El-Centro波时最大;上、下盘α 差值在输入Kobe波时最大;弯矩和桩顶相对位移峰值在输入Kobe波时最大;弯矩在土层分界面处较大,输入不同地震波时弯矩峰值均未超过桩身抗弯能力;提出了强震区近断层桩基可根据验算内容选取合理地震波进行验算的抗震设计建议。     

Stoichiometric saturation tests of NaCl1−xBrx and KCl1−xBrx

Stoichiometric saturation is examined as a possible control on Br contents of halite and sylvite during precipitation from binary salt solutions of NaCl-NaBr and KCl-KBr, respectively. Experimental data at 25°C, assumed to represent Stoichiometric saturation, were used to predict mole fractions of NaBr in halite and KBr in sylvite in thermodynamic equilibrium with fluids as a function of aqueous activity ratios of Br⁻:Cl⁻. The predictions are based on the additional assumption that the aqueous activity product of the major salt component in the precipitated salt was independent of the trace Br content in the salt lattice. The extension of the predictions to diagenetic pressures and temperatures is discussed.The predicted equilibrium Br content of halite at initial halite saturation of evaporating seawater is in close agreement with that computed from the distribution coefficient of Lutz (1975), measured in slowgrowth single crystal experiments. Fluid recrystallization of halite and sylvite at near-surface temperatures is predicted to generally deplete the Br contents in the solids. Bulk Br contents in halite in cap-rock of Gulf Coast salt domes generally agree with those predicted by the recrystallization of halite in the presence of evaporative-concentrated seawater. At a constant solution composition, increasing temperature results in increasing the equilibrium Br content of halite, making less efficient Br depletion in halite by recrystallization.     

全吸力范围生物炭−黏土混合土的土−水特性

土−水特征曲线在研究非饱和土的水力与力学特性中发挥着重要的作用。生物炭具有多孔结构、高比表面积和强吸附的特性。将生物炭改性土应用于垃圾填埋场上覆盖层,因受自然环境因素的影响会使其水力特性发生改变。为了研究全吸力范围内生物炭掺量对生物炭−黏土混合土保水特性的影响,利用蒸汽平衡法（吸力范围 3～368 MPa）、滤纸法（吸力范围 0 ～40 MPa）和压力板法（吸力范围 0～1.5 MPa）控制土样的吸力,测定吸力平衡后土样的含水率和饱和度,得到全吸力范围内生物炭−黏土混合土的土−水特征曲线。试验结果表明：（1）3种吸力测试方法很好地表达了生物炭−黏土混合土全吸力范围内的土−水特征曲线。（2）生物炭能够影响黏土的保水性,但在一定的吸力范围内,生物炭−黏土混合土的保水性还与孔隙结构和孔隙中水的形态相关。（3）通过压力板法测得,试样的进气值随着生物炭掺量的增加而减小。当吸力值小于进气值时,曲线出现水平段,土样始终处于饱和状态,生物炭掺量越大,试样的保水性越好。（4）由生物炭−黏土混合土微观孔隙结构以及生物炭在黏土中的分布形态来解释生物炭改性黏土的保水能力随生物炭掺量的变化关系。     

桩−筏基础中能量桩热−力耦合特性现场试验

能量桩兼具承担上部荷载和传递浅层地温能双重功能,能量桩的换热与承载特性逐渐成为广大工程技术人员关注的重点问题。然而,针对桩?筏基础中能量桩的热?力耦合特性的现场实测资料仍相对较少。提出将桩基完整性检测中的声测管底端连接贯通,作为能量桩的换热管,形成新型能量桩埋管形式;在桩?筏基础中能量桩运行状态下,开展桩?筏基础热力响应特性、能量桩对筏板应力影响的现场试验,实测获得桩身温度、桩身应力及筏板应力变化规律。研究结果表明,该试验条件下,能量桩（1U埋管、有效深度为12.8 m、桩顶埋深为5.5 m）的换热效率约为80～90 W/m;无上部荷载、能量桩加热状态下,筏板上边缘呈现出一定的拉应力,值得工程技术人员关注。     

Degradation of polyvinyl alcohol in aqueous solutions using UV-365 nm/S2O8 2− process

This investigation evaluates the effectiveness of UV-365 nm/S₂O₈ ^2? process in degrading polyvinyl alcohol in aqueous solutions. The effects of pH, Na₂S₂O₈ dosage, and temperature on the degradation efficiency of polyvinyl alcohol were studied. Under acidic conditions, the degradation efficiency of polyvinyl alcohol exceeded that under alkaline conditions. Additionally, a higher Na₂S₂O₈ dosage and a higher temperature were associated with a higher degradation efficiency of polyvinyl alcohol. The degradation rates of polyvinyl alcohol followed a pseudo-first-order kinetic model. Moreover, the observed degradation rate coefficient increased from 0.0078 to 0.4081 min^?1 when the temperature was increased from 10 to 55 °C. Also, the activation energy estimated using the observed degradation rate coefficients and the Arrhenius equation was 64 kJ/mol. At UV-365 nm, pH 3, an Na₂S₂O₈ dosage of 0.06 g/L, a temperature of 55 °C, and an initial polyvinyl alcohol concentration of 20 mg/L, around 100 % of polyvinyl alcohol was degraded, indicating that UV-365 nm/S₂O₈ ^2? process has great potential in degrading polyvinyl alcohol in aqueous solutions.     

High-density CO2−N2 inclusions in eclogite-facies metasediments of the Münchberg gneiss complex,SE Germany

The eclogite-facies metasedimentary rocks in the Münchberg gneiss complex (T=630±30° C/P17–24 kbar) locally contain CO₂–N₂-rich fluid inclusions of extremely low molar volumes (32 cm³/mol) in quartz. These fluid compositions are mainly found in rocks intercalated with calcsilicate bands. Densities were determined from low-temperature phase transitions like stable or metastable homogenization (L+VL), partial homogenization (S+L+VS+L) and the transition S+LL (L = liquid, V = vapour, S = solid). The high fluid densities are in agreement with eclogite-facies pressure and temperature and subsequent amphibolite facies. CO₂–N₂ inclusions were not observed in adjacent eclogites nor in non-calcareous metasediments. These rock types contain predominantly H₂O-rich inclusions correlating with amphibolite-facies conditions. The variation of fluid composition with lithological differences indicates local fluid gradients and speaks against a pervasive fluid flow during eclogite-facies metamorphism.     

活性氧化镁−微生物固化黄土试验研究

以活性氧化镁和微生物共同作用固化的黄土试样为研究对象,通过含水率、无侧限抗压强度、X射线衍射（XRD）和扫描电镜（SEM）等试验,研究了活性氧化镁掺量、养护龄期和初始含水率对固化试样含水率、无侧限抗压强度、固化产物和微观结构等的影响。结果表明：固化试样含水率随氧化镁掺量增加和养护龄期增长而降低;无侧限抗压强度随活性氧化镁掺量（5%～20%）增加而增大,随龄期发展总体上不断增大,但当氧化镁掺量为10%和15%时,后期强度稍有降低;当氧化镁掺量为5%和10%时,无侧限抗压强度随初始含水率增加而减小,而当氧化镁掺量为15%和20%时,无侧限抗压强度随初始含水率增加先增大后减小。XRD和SEM结果显示,随着氧化镁掺量增加,水化后未进一步反应的氢氧化镁越多;反应生成的水合碳酸镁具有膨胀性和胶结性,对土颗粒间缝隙进行填充,并将土颗粒胶结在一起。     

Thermodynamics of (Fe2+, Mn2+, Mg, Ca)3− Al2Si3O12 garnet: a review and analysis

Summary The thermodynamic properties of garnets in the system (Fe²⁺, Mn²⁺, Mg, Ca)₃A1₂Si₃O₁₂ are reviewed. The thermodynamic properties of the three end-member garnets pyrope, almandine and grossular, including their volume, enthalpy of formation, entropy, compressibility and thermal expansion have been well determined. For spessartine enthalpy of formation and heat capacity at low temperatures are needed. Pyrope's unusual behavior in some of its properties is probably related to the presence of the small, light Mg cation, which has a large anisotropic thermal vibration. The thermodynamic mixing properties of the six binaries are also discussed. Good volume of mixing data exist now for all of the binaries, but much work is still required to determine the enthalpies and third-law vibrational entropies of mixing. It is shown that the magnitude of the positive deviations in the volumes of mixing is related to the volume difference between the two end-member components. It is probable that excess entropies, if present, originate at low temperatures below 200 K. Recent²⁹Si NMR experiments have demonstrated the presence of short-range ordering (SRO) of Ca and Mg in pyrope-grossular solid solutions. Short-range order will have to be considered in new models describing the entropies of mixing. Its possible presence in all garnet solid solutions needs to be examined. The mixing properties of pyrope-grossular garnets, which are the best known for any garnet binary, can, in part, be described by the Quasi-Chemical approximation, which gives insight into the microscopic interactions which determine the macroscopic thermodynamic mixing properties. Microscopic properties are best investigated by spectroscopic and computational approaches. Hard mode IR measurements on binary solid solutions show that the range of local microscopic structural distortion is reflected in the macroscopic volumes of mixing. The nature of The contents of this contribution was presented at the IMA Meeting in Toronto in August, 1998. It precedes issues of Mineralogy and Petrology containing thematic sets of IMApapers strain tiields and site relaxation needs to be studied in order to obtain a better understanding of the solid-solution process and energetics in garnet. Critical areas for future experimentation are also addressed.[/p]

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Eine kritische Zusammenstellung und Analyse der thermodynamischen Daten der (Fe²⁺, Mn²⁺, Mg, Ca)₃Al₂Si₃O₁₂ granate

Zusammenfassung In dieser Studie werden die thermodynamischen Eigenschaften der Granate im System (Fe²⁺,Mn²⁺, Mg, Ca)₃Al₂Si₃O₁₂ kritisch zusammengestellt. Die thermodynamischen Eigenschaften der drei Endglied-Granate Pyrop, Almandin und Grossular, einschließlich ihrer Volumina, Bildungswärmen, Entropien, Kompressibilitäten und thermischen Ausdehnungen wurden bereits hinreichend gut bestimmt. Dagegen müssen die Bildungswärme und Tieftemperatur-Wärmekapazität von Spessartin noch gemessen werden. Die Eigenschaften des Pyrops sind wahrscheinlich mit den großen anisotropen Schwingungen des kleinen, leichten Mg-Kations verbunden. Die thermodynamischen Mischungseigenschaften der sechs binären Mischkristallreihen werden ebenfalls diskutiert. Während die Mischungs-Volumendaten der binären Mischreihen gut bekannt sind, müssen ihre Mischungs-Enthalpien und Standard-Mischungsentropien noch ermittelt werden. Es wurde gezeigt, daß die Größe der positiven Exzeß-Volumina mit dem Volumen-Unterschied der zwei Endglied-Komponenten der jeweiligen Mischreihe verknüpft ist. Es ist wahrscheinlich, daß Exzeß-Entropien, wenn vorhanden, erst bei Tieftemperaturen unter 200 K auftreten. Neue²⁹Si NMR-Experimente belegen, daß in Pyrop-Grossular-Mischkristallen Nahordnung von Mg und Ca vorliegt. Der Effekt der Nahordnung muß in künftigen thermodynamischen Modellen berücksichtigt werden. Hieraus ergibt sich die Notwendigkeit, alle Granat-Mischreihen auf mögliche Nahordnung hin zu untersuchen. Die Mischungseigenschaften der Pyrop-Grossular-Mischreihe, die von sämtlichen Granat-Mischreihen am besten bestimmt wurden, können teilweise mit dem Quasi-Chemical-Model beschrieben werden. Dieses Modell ermöglicht die Beschreibung der mikroskopischen Wechselwirkungen, die die makroskopischen thermodynamischen Eigenschaften bestimmen. Mikroskopische Eigenschaften werden am besten mit spektroskopischen Messungen und theoretischen Berechnungen untersucht. Hard-mode IR-Spektroskopie-Messungen an binären Mischreihen zeigen, daß die lokalen mikroskopischen strukturellen Verzerrungen in den makroskopischen Mischungs-Volumina widergespiegelt werden. Die Art der Spannungsfelder und Platz-Relaxationen muß detaillierter untersucht werden, um ein besseres Verständnis des Mischkristall-Bildungsprozsses und der Energetik der Granate zu erreichen. Darüber hinaus werden wichtige künftige Forschungsgebiete diskutiert.

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With 11 Figures     

Anticorrelated Rb−Sr and K−Ar age discordances,Leuchtenberg granite,NE Bavaria,Germany

The Leuchtenberg granite (Oberpfalz, NE Bavaria) displays a continuous differentiation trend ranging from mildy peraluminous, coarse-grained, porphyritic biotite granites (BG) to strongly peraluminous, medium- to fine-grained, garnet-bearing muscovite granites (GMG). The Rb–Sr and K–Ar age determinations of whole-rock and mineral samples from the granite and associated intermediate rocks (redwitzites) have revealed two divergent age gradients: Rb–Sr wholerock dates decrease and initial ⁸⁷Sr/⁸⁶Sr ratios increase for successively more evolved subsets of the granite. All BG samples (⁸⁷Rb/⁸⁶Sr=2–16) yield a date of 326±2 Ma with a low initial ⁸⁷Sr/⁸⁶Sr ratio of 0.70778±0.00013 (1), while all GMG samples (⁸⁷Rb/⁸⁶Sr=70 to 1000) yield a younger date of 317±2 Ma with an enhanced initial ⁸⁷Sr/⁸⁶Sr ratio of 0.7146±0.0039. The K–Ar measurements on biotites and muscovites give closely concordant dates for the GMG (326–323 Ma) and the southern lobe of the BG (324–320 Ma). The northern lobe of the BG, including the redwitzites, shows a well-defined trend of decreasing K–Ar dates from 320 Ma to 300 Ma towards the northwest. Critical consideration of both isotope systems leads to the conclusion that the Rb–Sr system of the GMG was disturbed by a later hydrothermal event. The ca. 326 Ma whole-rock Rb–Sr date for the BG is not in conflict with any of the K–Ar mineral dates and is taken as approaching the crystallization age of the Leuchtenberg granite. The K–Ar age progression within the northern lobe of the BG indicates that this part either cooled down over a protracted period of some 20 Ma or experienced reheating at ca. 300 Ma. The study highlights the potential of combined Rb–Sr and K–Ar dating in deciphering detailed chronology on the scale of a single igneous intrusion.     

Pyrolusite surface transformations measured in real-time during the reactive transport of Co(II)EDTA2−

Oxidation of Co(II)EDTA²⁻ to Co(III)EDTA⁻ by manganese and iron hydrous oxide minerals enhances the transport of ⁶⁰Co in subsurface environments. Until now, reduction of the oxidant MnO₂ has not been identified in hydrodynamic systems, leaving the fate and transport mechanisms involving ⁶⁰Co in natural environments unresolved. We investigated the transport of Co(II)EDTA²⁻ through packed beds of β-MnO₂ and identified the reaction mechanism using a novel hydrodynamic flow cell coupled with X-ray absorption near edge structure (XANES) spectroscopy. Using this technique we are able to determine both solution and solid-phase species of cobalt and manganese in real-time. Co(II)EDTA²⁻ is produced while Mn(IV) is reduced to Mn(III) which forms an α-Mn₂O₃layer on pyrolusite. This layer passivates the surface after an initial reaction period and ultimately limits the production of Co(III)EDTA⁻. As a consequence, the enhanced transport of ⁶⁰Co by oxidative processes may be diminished by continual exposure to pyrolusite—an advantage from an environmental quality perspective. It has also been clarified that Mn(III) is formed rather than Mn(II) resulting in formation of a stable trivalent manganese solid (α-Mn₂O₃).