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.     

大别杂岩中混合岩的矿物空间分布研究

介绍了矿物空间分布研究的基本原理及两种统计方法(接触频数法和线切法)。作者对混合岩矿物空间分布的研究表明:(1)前人提出的统计方法存在方法上的缺陷和应用上的局限性,作者推导出矿物接触类型的概率公式;(2)部分浅色体中矿物显示聚集分布的特征,而绝大部分的浅色体中矿物具有分散分布的特点。结合质量平衡和地球化学研究认为:大别杂岩中主体混合岩成因机制是重熔和交代作用。     

中国南方离子吸附型稀土矿床成矿类型及其母岩控矿因素探讨

传统认为中国南方的离子吸附型稀土矿床可划分为以“足洞式”为代表的重稀土型和以“河岭式”(或“花山式”)为代表的轻稀土型两种矿化类型。然而，近年来发现的许多矿床(如清溪、寨背和馒头山等)的赋矿风化壳中出现了轻稀土矿与重稀土矿并存现象，表现出特殊的“上轻下重”双层矿体结构。这指示了除重稀土型和轻稀土型之外，还存在着轻重稀土共生型的过渡类型。本研究通过对三种不同成矿类型的若干典型矿床系统对比，指出成矿类型的多样性与母岩性质密切相关，尤其是母岩的稀土元素地球化学和稀土载体矿物属性是制约成矿类型变化的关键因素。统计数据表明，从重稀土型→轻重稀土共生型→轻稀土型，成矿母岩的全岩稀土总量变化不大(ΣREY: 200×10-6~450×10-6→200×10-6~500×10-6→200×10-6~800×10-6)，但轻重稀土配分值出现较显著的区间性差异(ΣLREE/ΣHREY: 02~1→1~5→2~10)。与之同时，母岩中能为离子相稀土提供物源且具有重稀土配分属性的稀土副矿物类型和数量明显减少，这与全岩稀土元素地球化学特征中重稀土分量占比的降低趋势也互相匹配。该结果指示，以往认为重稀土配分母岩形成重稀土矿床、轻稀土配分母岩形成轻稀土矿床的传统观点需要外延，即一部分具有低度轻稀土配分属性(1＜ΣLREE/ΣHREY＜5)且含有丰富易风化稀土副矿物的母岩还可能形成轻重稀土共生型矿床，该认识可为今后离子吸附型稀土矿床勘查工作提供新的找矿依据。     

碳中和目标下关键矿产在清洁能源转型中的作用、供需分析及其建议

在"碳中和"目标的驱动下，全球能源系统向清洁化、低碳化甚至无碳化发展已是大势所趋。针对向清洁能源转型的需求，采用了统计对比、分类汇总、综合分析等方法，分析研究了关键矿产在电池、电网、低碳发电和氢能等行业中的作用和需求。结合当前关键矿产产量的地理集中度高、项目开发周期长、资源质量下降等矿产供应和投资计划不能满足清洁能源转型的需求等问题，提出确保关键矿产多样性供应，推动价值链各环节的技术创新，扩大回收利用，增强供应链弹性和市场透明度，将更高的环境、社会和治理标准纳入主流程及加强生产者和消费者之间的国际合作等建议。     

Interactive effects of the type of milling media and CuSO4 addition on the flotation performance of sulphide minerals from Merensky ore Part II: Froth stability

The limitations of pulp chemistry measurements in the flotation of a platinum group mineral (PGM) bearing Merensky ore were demonstrated in Part 1 of this article. In this paper the importance of the contribution of the froth structure due to changing froth stability is analysed using the batch flotation data. The effects of mild steel (MS) and stainless steel (SS) milling media and the addition of copper sulphate on the flotation performance of the sulphide minerals in Merensky ore have been evaluated in relation to the changes in stability of the froth phase. The effects of pulp chemistry and froth stability on the flotation of sulphide minerals were distinguished by using two different rate constants (k_t and k_w). The rate constant (k_w) calculated as a function of cumulative water recovery was used to describe characteristics of froth phase and k_t was calculated as a function of flotation time. The results revealed that the type of grinding media and copper sulphate addition had an interactive effect on the froth stability. While mild steel (MS) milling increased the froth stability due to the presence of hydrophilic iron hydroxides and colloidal metallic iron, the addition of copper sulphate reduced the stability, especially with stainless steel (SS) milling. Copper sulphate addition had a dual role in the flotation of Merensky ore in that it caused destabilisation of the froth zone as well as activation of selected sulphide minerals. The dominant effect was found to depend on the type of milling media and floatability of the mineral in question and this work has demonstrated the importance of using a combination of measurements to evaluate flotation performance holistically.     

Fluid salinities obtained by infrared microthermometry of opaque minerals: Implications for ore deposit modeling — A note of caution

Infrared microthermometry of opaque minerals has revealed that temperatures of phase changes vary with the infrared light source intensity, resulting in an overestimate of fluid salinities and an underestimate of homogenization temperatures. Failing to recognize this analytical artifact during infrared microthermometry may result in meaningless geological models. A fluid inclusion investigation on enargite from a high-sulfidation epithermal deposit is used as an example to document this. Fluid salinities obtained during an early investigation ranged between 6.3 and 20.4 wt.% NaCl, which were interpreted as intense boiling or as evidence for the involvement of a magmatic brine during ore formation. Fluid inclusion salinities obtained with improved analytical settings, i.e. low light intensities, fall between 1.1 and 1.7 wt.% NaCl and are in better agreement with fluid salinities obtained in quartz from similar deposits, and recent modeling suggesting vapor transport of Au and Cu from deep porphyry-Cu environments to shallower high-sulfidation epithermal deposits.     

Effects of magnetic interactions in anisotropy of magnetic susceptibility: Models, experiments and implications for igneous rock fabrics quantification

Besides granites of the ilmenite series, in which the anisotropy of magnetic susceptibility (AMS) is mainly controlled by paramagnetic minerals, the AMS of igneous rocks is commonly interpreted as the result of the shape-preferred orientation of unequant ferromagnetic grains. In a few instances, the anisotropy due to the distribution of ferromagnetic grains, irrespective of their shape, has also been proposed as an important AMS source. Former analytical models that consider infinite geometry of identical and uniformly magnetized and coaxial particles confirm that shape fabric may be overcome by dipolar contributions if neighboring grains are close enough to each other to magnetically interact. On these bases we present and experimentally validate a two-grain macroscopic numerical model in which each grain carries its own magnetic anisotropy, volume, orientation and location in space. Compared with analytical predictions and available experiments, our results allow to list and quantify the factors that affect the effects of magnetic interactions. In particular, we discuss the effects of (i) the infinite geometry used in the analytical models, (ii) the intrinsic shape anisotropy of the grains, (iii) the relative orientation in space of the grains, and (iv) the spatial distribution of grains with a particular focus on the inter-grain distance distribution. Using documented case studies, these findings are summarized and discussed in the framework of the generalized total AMS tensor recently introduced by Cañon-Tapia (Cañon-Tapia, E., 2001. Factors affecting the relative importance of shape and distribution anisotropy in rocks: theory and experiments. Tectonophysics, 340, 117–131.). The most important result of our work is that analytical models far overestimate the role of magnetic interaction in rock fabric quantification. Considering natural rocks as an assemblage of interacting and non-interacting grains, and that the effects of interaction are reduced by (i) the finite geometry of the interacting clusters, (ii) the relative orientation between interacting grains, (iii) their heterogeneity in orientation, shape and bulk susceptibility, and (iv) their inter-distance distribution, we reconcile analytical models and experiments with real case studies that minimize the role of magnetic interaction onto the measured AMS. Limitations of our results are discussed and guidelines are provided for the use of AMS in geological interpretation of igneous rock fabrics where magnetic interactions are likely to occur.     

The transition from peraluminous to peralkaline granitic melts: Evidence from melt inclusions and accessory minerals

Fractional crystallization of peraluminous F- and H₂O-rich granite magmas progressively enriches the remaining melt with volatiles. We show that, at saturation, the melt may separate into two immiscible conjugate melt fractions, one of the fractions shows increasing peraluminosity and the other increasing peralkalinity. These melt fractions also fractionate the incompatible elements to significantly different degrees. Coexisting melt fractions have differing chemical and physical properties and, due to their high density and viscosity contrasts, they will tend to separate readily from each other. Once separated, each melt fraction evolves independently in response to changing T/P/X conditions and further immiscibility events may occur, each generating its own conjugate pair of melt fractions. The strongly peralkaline melt fractions in particular are very reactive and commonly react until equilibrium is attained. Consequently, the peralkaline melt fraction is commonly preserved only in the isolated melt and mineral inclusions.

We demonstrate that the differences between melt fractions that can be seen most clearly in differing melt inclusion compositions are also visible in the composition of the resulting ore-forming and accessory minerals, and are visible on scales from a few micrometers to hundreds of meters.     

Atomistic calculations of structural and elastic properties of serpentine minerals: the case of lizardite

The physical properties of the hydrous phyllosilicate lizardite have been investigated by atomistic simulation using the GULP code based on transferable semi-empirical interatomic potentials. Lizardite behavior was first investigated during structure relaxation at room temperature. The Helmholtz free energy is minimum for an equilibrium structure that is in agreement with experiment. The bulk, shear, and Young modulii for lizardite were calculated along with the Poisson ratio. From the shear and bulk modulii, we also calculated translational and longitudinal acoustic wave velocities that are important quantities for tectonophysics models. As expected, lizardite is stiffer in the a direction parallel to the layers than in the c perpendicular direction; the variation of the unit cell parameters with pressure is in good agreement with experiment. The cohesive energy between two successive layers along c direction was calculated at 0.33 eV (i.e., 0.11 eV per OH bond) in good agreement with recent ab initio calculations. Upon pressure and temperature variations, we evidenced that structural changes are mainly pressure induced; pressure being accommodated by a decrease of the c parameter up to 10 GPa. We also found that the change of slope in the derivative of the c cell parameter with respect to pressure occurring around 2 GPa originates from the bending of the interlayer hydroxyl groups with respect to the layer normal direction.     

Comparison of magnetic parameters with vehicular Br levels in urban roadside soils

Chemical methods are generally chosen to monitor soil pollution but magnetic measurements proved to yield additional information at low cost and less time consumption. In this investigation, the novel use of rapid and non-destructive magnetic measurements to characterize Br levels in Xuzhou (China) urban roadside soils was reported. X-ray fluorescence spectrometry (XRF) was used to quantify Br in the soil samples. Data from 21 roadside soil samples confirm Br contamination, with a mean level of 4.36 mg kg⁻¹ and a range of 2.4–8.7 mg kg⁻¹. These values are higher than that of unpolluted soils in Xuzhou that averages 1.1 mg kg⁻¹. Hierarchical clustering analysis shows Br in Xuzhou roadside soils is mainly from road traffic. Clear correlations between Br levels and simple magnetic parameters [mass specific susceptibility (χ _LF), susceptibility of anhysteretic remanent magnetization (χ _ARM), saturation isothermal remanence (SIRM)] are observed. The present study shows that these three magnetic parameters can be used as a proxy for Br levels in Xuzhou urban roadside soils.