Interplay between equilibrium and kinetics in prograde metamorphism of pelites: an example from the Nelson aureole, British Columbia

The distribution of metapelitic mineral assemblages in the Nelson aureole, British Columbia, generally conforms to what is predicted from phase equilibria. However, in detail, the sequence and spacing of isograds, mineral textures and mineral compositions and mineral chemical zoning do not. Two of the main disequilibrium features in the aureole are: (i) delay in the onset and progress of several reactions, i.e. overstepping in temperature; and (ii) unreactivity of staurolite and especially garnet porphyroblasts when they are reactants in prograde reactions. The thermal overstepping is ascribed to difficulty of nucleation of the product porphyroblasts and sluggishness of dissolution of porphyroblasts when they are reactants. The extent to which these kinetic barriers delay the onset of reaction is related to the reaction affinity of each reaction, defined herein as the Gibbs free‐energy difference between the thermodynamically stable, but not‐yet‐crystallized, products and the metastable reactants. For oversteps in temperature (ΔT), reaction affinity is, in turn, related to the difference in entropy (ΔS) between these two states through the relation A = ΔT * ΔS. Mineral reactions which release large quantities of H₂O, such as chlorite‐consuming reactions, have a higher entropy change per unit of temperature overstep, and therefore a higher reaction affinity, than those which release little or no H₂O, such as the chlorite‐free staurolite‐consuming reaction. Thermal overstepping is consequently expected to be less for the former than for the latter, as was estimated in the aureole where 0 to 30 °C overstepping was required for garnet, staurolite and andalusite growth from a muscovite + chlorite‐bearing precursor rock and ～70 °C overstepping was required for the growth of Al₂SiO₅ from a staurolite‐bearing, chlorite‐free precursor. In all cases, reaction progress was strongly influenced by the presence or absence of fluid, with presence of fluid lowering kinetic barriers to nucleation and growth and therefore the degree of thermal overstepping. Textural features of rocks from the nearly coincident garnet, staurolite and andalusite isograds are suggestive of a fluid‐catalysed ‘cascade effect’ in which reaction took place in a narrow temperature interval; several competing muscovite + chlorite‐consuming reactions, some metastable, appear to have occurred in parallel. Metamorphic reaction, fluid release and possibly fluid presence in general in the aureole were episodic rather than continuous, and in several cases well removed from equilibrium conditions. The extent to which these findings apply to regional metamorphism depends on several factors, a major one being enhanced deformation, which is expected to lower kinetic barriers to nucleation and growth.     

Stable Isotope and Element Geochemistry of Saline Springs in Evaporite-bearing Mengla Basin,South Yunnan,China

正1 Introduction Mengla Basin is a sub-basin in southern evaporitebearing Lanping-Simao Basin.There are many salt springs in the basin.In 2012,11 spring samples were collected for analyses of chemistry and boron,hydrogen and oxygen     

Trace element and sulfur isotopic evidence for redox changes during formation of the Wallaby Gold Deposit,Western Australia

Wallaby is a major gold deposit of the St Ives Gold field of Western Australia, with an estimated resource of 8 million ounces of gold. It has a well-established paragenesis across five vein sets that displays macroscopic evidence of changing redox through time; from hematite to magnetite. Micro-analysis of pyrite from each vein generation shows a progressive and gradual change in redox conditions. The sulfur isotope composition has a δ³⁴S range of −7.7 to +9.8‰ using 3 μm spots on the Sensitive High Resolution Iron Micro Probe-Stable Isotope (SHRIMP-SI). Negative values indicative of an oxidized sulfur signature are found in the earliest generation of pyrite (which coexists with hematite) that also contains high concentrations of As, Ni, Zn, Ag, Sb, Cu and Pb. Conversely, positive values representative of reduced sulfur are found in later generations of pyrite, with lower concentrations of As, Ni, Sb, Cu, Zn and Pb. These later pyrite crystals display higher As/Ni, As/Sb, and As/Bi, and lower Cu/Te. These geochemical trends are the result of redox controlled transport and partitioning into pyrite of minor and trace elements now within the pyrite structure. Previous studies suggested a single orogenic event formed the Wallaby Deposit. This is not supported by the present study. Trace element ratios such as As/Ni clearly delineate the high Au generations and could be used as an exploration tool. It is suggested that pyrite from the Wallaby Gold Deposit formed via desulfidation and a gradual change in redox conditions within an evolving fluid and did not result from mixing of two separate fluids as previously advocated. Utilizing pyrite to link the entire fluid history of Wallaby demonstrates the general use of pyrite as a valuable mineral tracer in gold-bearing fluid systems.     

The relation between electric and redox potential: evidence from laboratory and field measurements

In field and laboratory experiments the relationship of redox, electric, and total potential was studied. This was carried out by using different arrangements of Pt and Ag/AgCl electrodes. The total potential is obtained by placing a Pt and an Ag/AgCl electrode at considerable distance apart on the rock. The studies indicate that the total potential yields the sum of redox and electric potential. Deviations larger than a couple of mV are caused by extensive fluid–rock interactions. In the laboratory it is seen that the magnitude of the electric potential is generally not larger than the artificially produced difference of the redox potential. The former is most likely attributed to a diffusion or membrane potential. At field scale the electric potential is designated as self potential. Redox potential measurements in the field may supply information from remnants of pore fluid of the rock and thereby may be suitable to support the exploration of concealed metal deposits. Detectable are in particular the fast H⁺ ions which are released by electrochemical reactions and transported by electromigration, both of which are attributed to the presence of the so called geobattery.     

矿物表面基团与表面作用

矿物的表面或界面过程存在于一切地质过程中,并在材料和环境科学领域得到广泛应用。矿物的表面结构、表面基团与表面作用之间存在着一定的内在联系,矿物结构的多样性决定了表面基团类型的多种性和表面作用的多样性。本文较系统地介绍了矿物表面功能基、表面配位反应、表面配合反应、表面氧化还原反应、表面异位催化反应和表面离子交换反应的类型及作用机制。     

Utilization of Lime for Stabilizing Soft Clay Soil of High Organic Content

This paper presents the results of geotechnical and mineralogical investigations on lime-treated soft clay soil from Idku City, Egypt, where high organic matters of about 14% exist. Lime was added in the order of 1%, 3%, 5% and 7% by weight and laboratory experiments after 7, 15, 30 and 60 days were conducted including the mineralogical and microstructural examinations, grain size analysis, plasticity limits, unconfined compressive tests, vane shear tests and oedometer tests. The results indicate that soft clay soil of high organic content of 14% can be stabilized satisfactorily with the addition of 7% lime. The results also demonstrate that the changes in the mineralogical contents and soil fabric of high organic lime-treated soft clay improve soil plasticity, strength and compressibility.     

视剖面图温压计研究进展评述

视剖面图温压计是目前定量估算变质温度和压力的主要方法之一。其理论基础为热力学平衡原理与质量守恒定律。利用内恰的热力学数据库和相应的成分-活度模型对特定成分体系进行视剖面图计算,可以正演模拟给定温度和压力条件下的矿物组合、矿物丰度及其成分,与实测岩石对比,可以准确获取岩石的形成温度和压力。在应用视剖面图温压计时,应选择受全岩成分影响小、且受退变质作用影响微弱的矿物成分;对于有成分变化的体系,应结合多种方法恢复有效全岩成分。文中通过视剖面图对KFMASH(K2O-Fe O-Mg O-Al2O3-Si O2-H2O)体系下不同矿物组合内多硅白云母硅含量及其等值线斜率的研究,认为多硅白云母硅含量及其等值线斜率主要由不同矿物组合内多硅白云母参与的契尔马克替换及纯转换端元反应中的主导反应决定,进一步深化了对变质过程中控制矿物成分变化的内部缓冲反应机制的理解,从而也可为选择和应用矿物温压计提供指导。因此,视剖面图方法是目前研究变质岩石形成条件及变质作用精细过程的最佳方法之一。     

Long-term performance evaluation of zero-valent iron amended permeable reactive barriers for groundwater remediation – A mechanistic approach

Permeable reactive barriers (PRBs) are used for groundwater remediation at contaminated sites worldwide. This technology has been efficient at appropriate sites for treating organic and inorganic contaminants using zero-valent iron (ZVI) as a reductant and as a reactive material. Continued development of the technology over the years suggests that a robust understanding of PRB performance and the mechanisms involved is still lacking. Conflicting information in the scientific literature downplays the critical role of ZVI corrosion in the remediation of various organic and inorganic pollutants. Additionally, there is a lack of information on how different mechanisms act in tandem to affect ZVI-groundwater systems through time. In this review paper, we describe the underlying mechanisms of PRB performance and remove isolated misconceptions. We discuss the primary mechanisms of ZVI transformation and aging in PRBs and the role of iron corrosion products. We review numerous sites to reinforce our understanding of the interactions between groundwater contaminants and ZVI and the authigenic minerals that form within PRBs. Our findings show that ZVI corrosion products and mineral precipitates play critical roles in the long-term performance of PRBs by influencing the reactivity of ZVI. Pore occlusion by mineral precipitates occurs at the influent side of PRBs and is enhanced by dissolved oxygen and groundwater rich in dissolved solids and high alkalinity, which negatively impacts hydraulic conductivity, allowing contaminants to potentially bypass the treatment zone. Further development of site characterization tools and models is needed to support effective PRB designs for groundwater remediation.     

Subterranean microorganisms and radioactive waste disposal in Sweden

In 1987, microbiology became a part of the Swedish scientific program for the safe disposal of high level nuclear waste (HLW). The goal of the microbiology program is to understand how subterranean microorganisms will interact with the performance of a future HLW repository. The Swedish research program on subterranean microbiology has mainly been performed at two sites in granitic rock aquifers at depths ranging from 70 m down to 1240 m, the Stripa research mine in the middle of Sweden and the Äspö Hard Rock Laboratory (HRL) situated on the south eastern coast of Sweden. Some work has also been performed in cooperation with other national or international research groups in Sweden, Canada and at the natural analogue sites Oklo in Gabon and Maqarin in Jordan. The following conclusions are drawn. There is a very high probability of the existence of a deep subterranean biosphere in granitic rock. The documented presence of a deep biosphere implies that relevant microbial reactions should be included in the performance assessment for a HLW repository. A HLW repository will be situated in a subterranean biosphere that is independent of solar energy and photosynthetically produced organic carbon. The ultimate limitation for an active microbial life will be the availability of hydrogen as energy source over time, and hydrogen has indeed been found in most deep groundwaters. Sulphide producing microorganisms are active in environments typical for a Swedish HLW repository, and the potential for microbial corrosion of the copper canisters must be considered. The bentonite buffer around the copper canisters will be a hostile environment for most microbes due to the combination of radiation, heat and low water availability. Discrete microbial species can cope with each of these constraints, and it is theoretically possible that sulphide producing microbes may be active inside a buffer, although the experiments conducted thus far have shown the opposite. Microorganisms have the capability to enzymatically recombine radiolysis oxidants formed by radiation of water. It has earlier been concluded that the migration of radionuclides due to sorption on microorganisms can be neglected. The influence of microbially produced complexing agents remains to be studied at realistic conditions in deep groundwater. Microorganisms have been found in natural alkaline groundwaters, but it could not be conclusively demonstrated that they were in situ viable and growing, rather than just transported there from neutral groundwater. A possible hypothesis based on the obtained results from investigations of natural alkaline groundwaters is that fresh concrete may be a bit too extreme for active life even for the most adaptable microbe – but this remains to be demonstrated.     

Chemical characterization of the Neogene Aquifer, Belgium

The evolution of groundwater chemistry along the direction of groundwater flow was studied using hydrochemical data from samples collected along a flow line in the Neogene Aquifer, Belgium. Infiltrating water was found to have a very low mineral content and low pH because the sediments are strongly decalcified. Increasing SiO₂ and cation concentrations along the groundwater flow line indicate silicate-weathering processes, confirmed with the aid of saturation indices, calculated with PHREEQC, and stability diagrams. A classification system based on redox sensitive species was developed and shows that an extensive redox sequence is present in the aquifer. At a shallow depth, pyrite oxidation has caused an increase in sulphate, while iron is precipitated as hydroxides. Elevated arsenic concentrations are related to the reduction of these iron hydroxides at a relatively shallow depth and to the dissolution of siderite at greater depth. Dissolution of carbonate in the aquifer material, present in deep layers and to the north, has lead to increased Ca²⁺ and HCO₃ ^? concentrations. The Ca²⁺ from the groundwater is exchanged for Na⁺, Mg²⁺ and K⁺ adsorbed to the clay surfaces at the bottom of the groundwater reservoir. Although the Neogene Aquifer is well flushed, there are still some marine influences present in the deepest parts.