Precipitation of poorly crystalline antigorite under hydrothermal conditions

Magnesium silicate precipitation experiments were carried out in alkaline solutions in the temperature range 39°C-150°C. Titrations were carried out at room temperature where the pH of an aqueous solution containing magnesium and silica was raised to bring about precipitation of a magnesium silicate. The precipitation of the magnesium silicate was rapid. Equilibrium between the solution and the precipitate was attained in a period of less than one hour up to a month at around 90°C, depending on the initial degree of oversaturation. Relative magnesium and silica depletion in the experimental solutions and IR spectra of the precipitate show that the magnesium silicate resembles poorly developed antigorite (p-antigorite). Values for its solubility constant were obtained and an equation describing its solubility in the temperature interval 0°-200°C calculated. The equation is: log K_sp = 9303/T + 3.283, where T is in K, and it is valid for the following reaction:

     

The reaction kinetics of alanine and glycine under hydrothermal conditions

Experimental data on the hydrothermal reaction kinetics of α-alanine, glycine, and β-alanine were acquired using a custom-built spectrophotometric reaction cell which permits in situ observation under hydrothermal conditions. Quantitative kinetic information, including rate constants, concentration versus time profiles, and calculations of the individual component spectra, was obtained from the data using a self-modeling chemometric approach based on factor analysis which treats the rate expressions simultaneously as a system of differential algebraic equations (DAE) of index 1. Experimental data collected at 120-165 °C and 20 bar indicates that aqueous α-alanine, glycine and β-alanine will preferentially undergo dimerization and subsequent cyclization when heated in an inert reactor. The results presented here lend further support to the roles of temperature, exposed reactive surfaces, and matrix additives in the reaction kinetics of the structurally simple amino acids examined in this study.     

Structure and properties of loaded silica contacts during pressure solution: impedance spectroscopy measurements under hydrothermal conditions

In order to investigate directly the structure and properties of grain boundaries in silicate materials undergoing pressure solution, in situ measurements of these properties are required. We report electrical impedance spectroscopy measurements, performed, under hydrothermal conditions, on individual glass–glass and glass-quartz contacts undergoing pressure solution. Resulting estimates of the average grain boundary diffusivity product ( Z = Dd_\textav C^* Z = D\delta_{\text{av}} C^{*} ) for silica transport and of the average grain boundary fluid film thickness ( d_\textav \delta_{\text{av}} ) fall in the ranges 6.3 ± 1.4 × 10⁻¹⁸ m³ s⁻¹ and 350 ± 210 nm, respectively. However, the average values for Z and d_\textav \delta_{\text{av}} obtained were likely influenced by cracking and irregular dissolution of the dissolving contact surfaces, rather than representing uniformly wetted grain boundary properties. Post-mortem SEM observations indicate that the contact surfaces were internally rough. Taken together, our data support the notion that during pressure solution of quartz, grain boundary diffusion is rapid, and interface processes (dissolution and precipitation) are more likely to be rate-limiting than diffusion.     

Frictional sliding of gabbro gouge under hydrothermal conditions

We investigated the frictional sliding behaviour of gabbro gouge under hydrothermal conditions. Experiments were performed on 1-mm-thick gabbro gouge sandwiched between country rock pieces (with gouge inclined 35° to the sample axis) in a triaxial testing system with argon gas as the confining medium. In the first series, experiments were conducted under effective normal stresses of 200 MPa and 300 MPa respectively, with pore pressure of 10 MPa. For temperature over 400 °C, pore pressure of 30 MPa was also applied to implement supercritical water conditions. At temperatures up to 615 °C, slip rate steps ranging from 0.0488 μm/s to 1.22 μm/s were applied to obtain the rate dependence of friction.At 200 MPa effective normal stress and a pore pressure of 10 MPa, the steady state rate dependence a–b shows velocity-weakening behaviour for temperatures between  200 and  310 °C. The higher temperature limit for velocity-weakening behaviour to occur extends up to  510 °C under supercritical water conditions with a pore pressure of 30 MPa. For the limited sliding distance in our experiments, only velocity-strengthening behaviour occurred at 300 MPa effective normal stress. Considering the limited displacement (< 3.5 mm), velocity-weakening behaviour may not be excluded in the high effective normal stress case for temperature below  510 °C.The coefficient of friction shows an increasing trend with increasing temperature in the low temperature range. The cut-off temperatures for the increasing trend are  250 °C and  440 °C, respectively for the 200 MPa and 300 MPa effective normal stress cases. Above the cut-off temperatures, the coefficient of friction at 1.83 mm permanent displacement varies around an average of 0.73, which is identical to the average for the oven-dried case [He, C., Yao, W., Wang, Z., Zhou, Y., 2006. Strength and stability of frictional sliding of gabbro gouge at elevated temperatures. Tectonophysics 427, 217–229, doi:10.1016/j.tecto.2006.05.023]. Together with the small value of rate dependence (a–b < 0.0073) for the whole temperature range, these results indicate the absence of fluid-assisted creep.With the result of our experiments as a constraint on strength of frictional sliding, comparison between converted strength for strike–slip faults and creep strength of gabbro-like rocks implies fracturing and faulting behaviours in the lower crust of a cool area (Zhangbei) in North China.     

Experimental investigation of single carbon compounds under hydrothermal conditions

The speciation of carbon in subseafloor hydrothermal systems has direct implications for the maintenance of life in present-day vent ecosystems and possibly the origin of life on early Earth. Carbon monoxide is of particular interest because it represents a key reactant during the abiotic synthesis of reduced carbon compounds via Fischer-Tropsch-type processes. Laboratory experiments were conducted to constrain reactions that regulate the speciation of aqueous single carbon species under hydrothermal conditions and determine kinetic parameters for the oxidation of CO according to the water water-gas shift reaction (CO₂ + H₂ = CO + H₂O). Aqueous fluids containing added CO₂, CO, HCOOH, NaHCO₃, NaHCOO, and H₂ were heated at 150, 200, and 300 °C and 350 bar in flexible-cell hydrothermal apparatus, and the abundances of carbon compounds was monitored as a function of time. Variations in fluid chemistry suggest that the reduction of CO₂ to CH₃OH under aqueous conditions occurs via a stepwise process that involves the formation of HCOOH, CO, and possibly CH₂O, as reaction intermediaries. Kinetic barriers that inhibit the reduction of CH₃OH to CH₄ allow the accumulation of reaction intermediaries in solution at high concentrations regulated by metastable thermodynamic equilibrium. Reaction of CO₂ to CO involves a two-step process in which CO₂ initially undergoes a reduction step to HCOOH which subsequently dehydrates to form CO. Both reactions proceed readily in either direction. A preexponential factor of 1.35 × 10⁶ s⁻¹ and an activation energy of 102 kJ/mol were retrieved from the experimental results for the oxidation of CO to CO₂. Reaction rates amongst single carbon compounds during the experiments suggest that ΣCO₂ (CO₂ + HCO₃⁻ + CO₃²⁻), CO, ΣHCOOH (HCOOH + HCOO⁻), and CH₃OH may reach states of redox-dependent metastable thermodynamic equilibrium in subseafloor and other hydrothermal systems. The abundance of CO under equilibrium conditions is strongly dependent on temperature, the total carbon content of the fluid, and host-rock lithology. If crustal residence times following the mixing of high-temperature hydrothermal fluids with cool seawater are sufficiently long, reequilibration of aqueous carbon can result in the generation of additional reduced carbon species such as HCOOH and CH₃OH, and the consumption of H₂. The present study suggests that abiotic reactions involving aqueous carbon compounds in hydrothermal systems are sufficiently rapid to influence metabolic pathways utilized by organisms that inhabit vent environments.     

Topotactic formation of ferrisicklerite from natural triphylite under hydrothermal conditions

The topotactic oxidation and delithiation reaction from triphylite, Li(Fe,Mn)PO₄, leading to ferrisicklerite, Li_<1(Fe³⁺,Mn²⁺)PO₄, was investigated under hydrothermal conditions. A cuboid cut from a triphylite single-crystal (Palermo Mine, New Hampshire, USA) with the composition Li_0.93(3)(Fe²⁺ _0.733(6),Fe³⁺ _0.015(1),Mn²⁺ _0.210(4),Mg_0.063(2))_1.021(8)P_1.00(2)O₄ in addition with ground bulk material were treated with KMnO₄ and 30 % H₂O₂(aq) as oxidizing agent in a 0.1 N hydrochloric acid solution in the temperature range between 60 and 200 °C. At 120 °C a rim of 0.1 mm thickness of ferrisicklerite had formed around the core of unreacted triphylite. The sharp reaction boundary was clearly visible, due to the reddish brown absorption colors of ferrisicklerite, compared to colorless triphylite. Using single-crystal X-ray diffraction (XRD), secondary ion mass spectrometry (SIMS), electron probe micro-analysis (EPMA) and ⁵⁷Fe-Mössbauer spectroscopy the product ferrisicklerite was characterized and its composition determined as Li_0.30(7)(Fe²⁺ _0.049(1)Fe³⁺ _0.65(2)Mn²⁺ _0.218(5)Mg_0.062(2))_0.98(1)P_1.01(3)O₄, with unit cell parameters a?=?4.795(1), b?=?9.992(4), and c?=?5.886(2) Å. EPMA investigations across the reaction boundary showed no changes in the concentrations of Fe, Mn, Mg, and P. In contrast, SIMS measurements clearly proved the delithiated state of the ferrisicklerite product. Polarization microscopy revealed that the orientation of the ferrisicklerite rim was the same as that of the original triphylite single-crystal, confirming the strictly topotactic character of the reaction.     

Crystal structure of nitrate cancrinite synthesized under low-temperature hydrothermal conditions

Doklady Earth Sciences -     

Dissolution-precipitation reactions controlling fast formation of dolomite under hydrothermal conditions

In laboratory experiments, the precipitation of dolomite at ambient temperature is virtually impossible due to strong solvation shells of magnesium ions in aqueous media and probably also due to the existence of a more intrinsic crystallization barrier that prevents the formation of long-range ordered crystallographic structures at ambient surface conditions. Conversely, dolomite can easily form at high temperature (>100 °C), but its precipitation and growth requires several days or weeks depending on experimental conditions. In the present study, experiments were performed to assess how a single heat-ageing step promotes the formation of dolomite under high-carbonate alkaline conditions via dissolution-precipitation reactions. This reaction pathway is relevant for the so-called hydrothermal dolomite frequently observed in carbonate platforms, but still ill-defined and understood. Our precipitation route is summarized by two main sequential reactions: (1) precipitation of Mg-calcite at low temperature (∼20 °C) by aqueous carbonation of synthetic portlandite (Ca(OH)₂) in a highly alkaline medium (1 M of NaOH and 1 M of MgCl₂), leading to precipitation of oriented nanoparticles of low- and high-Mg calcite (∼79 wt%) coexisting with aragonite (∼18 wt%) and brucite (∼3 wt%) after 24 h; (2) fast dolomitization process starting from 1 h of reaction by a single heat-ageing step from ∼20 to 200, 250 and 300 °C. Here, the Mg-calcite acts as a precursor that lowers the overall kinetics barrier for dolomite formation. Moreover, it is an important component in some bio-minerals (e.g. corals and seashells). Quantitative Rietveld refinements of XRD patterns, FESEM observations and FTIR measurements on the sequentially collected samples suggest fast dolomite precipitation coupled with dissolution of transient mineral phases such as low-Mg calcite (Mg < 4 mol%), high-Mg calcite (Mg > 4 mol%), proto-dolomite (or disordered dolomite; Mg > 40 mol%) and Ca-magnesite. In this case, the dolomite formation rate and the time-dependent mineral composition strongly depend on reaction temperature. For example, high-purity dolomitic material (87 wt% of dolomite mixed with 13 wt% of magnesite) was obtained at 300 °C after 48 h of reaction. Conversely, a lower proportion of dolomite (37 wt%), mixed with proto-dolomite (43 wt%), Ca-magnesite (16 wt%) and high-Mg calcite (4 wt%), was obtained at 200 °C after 72 h. The present experiments provide an additional mechanism for the massive dolomite formation in sedimentary environments (ex. deep sea organic-rich carbonate-sediments) if such sediments are subjected to significant temperature variations, for example by hot fluid circulations related to volcanic activity. In such systems, organic degradation increases the carbonate alkalinity (HCO₃⁻) necessary to induce the dolomitization process at low and high temperature.     

The mechanism of cation and oxygen isotope exchange in alkali feldspars under hydrothermal conditions

The mechanism of re-equilibration of albite in a hydrothermal fluid has been investigated experimentally using natural albite crystals in an aqueous KCl solution enriched in ¹⁸O at 600°C and 2 kbars pressure. The reaction is pseudomorphic and produces a rim of K-feldspar with a sharp interface on a nanoscale which moves into the parent albite with increasing reaction time. Transmission electron microscopy (TEM) diffraction contrast and X-ray powder diffraction (XRD) show that the K-feldspar has a very high defect concentration and a disordered Al, Si distribution, compared to the parent albite. Raman spectroscopy shows a frequency shift of the Si-O-Si bending vibration from ~476 cm⁻¹ in K-feldspar formed in normal ¹⁶O aqueous solution to ~457 cm⁻¹ in the K-feldspar formed in ¹⁸O-enriched solution, reflecting a mass-related frequency shift due to a high enrichment of ¹⁸O in the K-feldspar silicate framework. Raman mapping of the spatial distribution of the frequency shift, and hence ¹⁸O content, compared with major element distribution maps, show a 1:1 correspondence between the reaction rim formed by the replacement of albite by K-feldspar, and the oxygen isotope re-equilibration. The textural and chemical characteristics as well as the kinetics of the replacement of albite by K-feldspar are consistent with an interface-coupled dissolution-reprecipitation mechanism.     

硅桥问题——兼及当代热液成矿理论的概念更新

硅的地球化学是热液成矿理论网络中最重要的横向沟通桥粱之一。我们平日千百万次看到的一个最普通的矿物——石英却蕴藏了相当丰富的内涵．通过它可以把表面上几乎毫不相关的各个矿床和矿化类型联络成为一个巨系统。本文拟尝试提出一个热液成矿过程的新流程：HACONSA→RE(HCONS)→E+SiO₂，H为氢，卤素(主要是氟、氯，也包括溴、碘)，也代表热，A为碱金属（主要是钾、钠，还包括锂、铷、铯）；C为碳；O为氧；N为氮；S为硫族（包括Se、Te）。HACONS可简称幔汁，它是对文献中地幔热流体的地球化学结构的确切陈述。R为岩石（主要指地壳岩石），E为成矿元素，SiO₂为氧化硅（其矿物形式为石英、蛋白石、玉髓、燧石、碧玉，也包括蚀变中的硅化和沉积岩中的硅质层）。发自地幔的热流体沿深大断裂系统上涌进入地壳，混入地壳物质，其中的钠、钾等通过碱交代作用破坏岩石，释放成矿元素，后者被酸性挥发分（或称矿化剂）络合迁移，到减压、降温、中和区（陆上或海底）成矿元素和硅质发生沉淀、富集或成矿。     

Molybdic acid ionisation under hydrothermal conditions to 300 °C

This UV spectrophotometric study was aimed at providing precise, experimentally derived thermodynamic data for the ionisation of molybdic acid (H₂MoO₄) from 30 to 300 °C and at equilibrium saturated vapour pressures. The determination of the equilibrium constants and associated thermodynamic parameters were facilitated by spectrophotometric measurements using a specially designed high temperature optical Ti-Pd flow-through cell with silica glass windows.The following van’t Hoff isochore equations describe the temperature dependence of the first and second ionisation constants of molybdic acid up to 300 °C:

     

白炭黑的应用与制备方法

白炭黑作为许多新材料的重要组元,已经被广泛研究。本文系统地描述了白炭黑在工业中的应用,并介绍了现有的白炭黑制备方法,如以蒙脱石为原料的碱浸法、以四氯化硅为原料的气相法、以水玻璃为原料的沉淀法等。对各种方法对比发现,提高沉淀法白炭黑的性能,使之接近气相法白炭黑,是今后白炭黑生产的重要发展方向。     

Leaching and differential recrystallization of metamict zircon under experimental hydrothermal conditions

We report results of hydrothermal experiments on four alluvial zircons from Sri Lanka, which cover a wide range of radiation damage, at 450 °C and 1.3 kbar for 744 h with 2 M CaCl₂ solution as reactive fluid. After the hydrothermal treatment, the most metamict samples show micrometer-thick reaction rims, which surround apparently unreacted zircon, as revealed by cathodoluminescence (CL) and Nomarski differential interference contrast (NDIC) images. These rims have sharp, curved, and transgressive boundaries with unreacted zircon and are, in some cases, spread out along cracks. The thickness of reaction rims increases with increasing cumulated !-dosage of the starting materials. The reaction rims are strongly enriched in Ca (up to 7000 ppm) and a water species and depleted in radiogenic Pb, Zr, and Si, as revealed by electron microprobe analyses. A significant Th loss from the reaction rims was detected in the case of the most metamict sample, whereas U remained in the structure. FT-infrared spectrometry and X-ray diffraction measurements revealed that the bulk run products were recrystallized. Using micro-Raman spectrometry, we were able to demonstrate that differential recrystallization took place. The reaction rims are strongly recrystallized, whereas the unreacted grain interiors underwent only minor recrystallization. Recrystallization of the rims is accompanied by an enhancement of the integral CL intensity. It is suggested that recrystallization in the reaction rims was catalyzed by water infiltration and ion exchange and prevented significant congruent zircon dissolution under the given experimental conditions. Previous zircon studies have shown that (1) a transgressive morphology, (2) a reduced Th-U ratio, and (3) an enhanced CL emission are also characteristics of rims in zircons from high-grade metamorphic rocks. Based on these similarities between natural and experimentally produced rims, it is suggested that leaching-catalyzed recrystallization is an important alteration process in zircon under wet geological conditions and can account for many complex core-rim structures found in natural zircons. Furthermore, the strong enrichment of Ca in the reaction rims supports previous assumptions that high Ca concentrations in natural zircons are of secondary origin. It is suggested that lower U-Pb concordia intercept ages obtained from single-phase zircons with high Ca contents date a leaching event.     

Bacterially-mediated weathering of crystalline and amorphous Cu-slags

Two types of Cu-slags (CS: crystalline massive slag and GS: granulated amorphous slag) exhibiting a different chemical and mineral phase composition were compared with respect to their susceptibility to bacterial weathering using Pseudomonas aeruginosa (n° CIP 105094). Abiotic conditions e.g. sterile growth medium and ultrapure water were used for comparison. The experiments were extended up to 112 days with a systematic liquid phase renewal every 14 days. The results revealed significant release of elements in the bacterially mediated weathering experiments. Concentrations of elements (Si, Fe, Cu, Zn and Pb) in the biotic solutions were increased at least by 20% up to 99% compared to abiotic ones. From 3 to 77% of the leached elements were associated to the fraction >0.22 μm. Scanning electron microscope observations demonstrated greater weathering of mineral phases in biotic experiments than in abiotic ones which is in accordance with the solution chemistry exhibiting higher concentrations of elements leached in biotic set-ups. In the case of CS, glass and sulfides weathering was yet observed in abiotic experiment, whereas partial dissolution of fayalite (Fe₂SiO₄) was solely affected by the presence of bacteria. GS having a higher bulk content of metallic elements was found to be more stable than sulfide-bearing CS, while its (GS) glass matrix was found to weather easier under biotic conditions.     

石英高压相变研究进展

文中总结了前人有关石英高温高压相变的实验结果。根据以前的实验,在静水压条件下,石英-柯石英-斯石英-CaCl2结构超斯石英相-α-PbO2结构超斯石英相之间的相变方程分别是:p(GPa)=(2.11±0.03)+(9.8×10-4±1.2×10-4)×T(℃),p(GPa)=(8.0±0.2)+(1.1×10-3±3×10-4)×T(℃),p(GPa)=(51±2)+(0.012±0.005)×T(K),p(GPa)=98+(0.0095±0.0016)×T(K)。文中还初步探讨了非静水压状态对石英相变的影响。实验结果表明,差应力的出现降低了石英相变所需要的围压,即相变边界向低压方向偏移,在周永胜等人实验数据的基础上,笔者尝试将二维的相图扩展到三维相图以考虑差应力的影响。最后讨论了石英相变在地学研究中的作用,对比不同的观点分析了前人对超高压变质作用过程的解释,希望可以为以后解释地质资料提供较为广泛的可能性,促进我们对地球内部动力学过程的了解。     

A geochemical clogging model with carbonate precipitation rates under hydrothermal conditions

A step-wise numerical calculation method was developed to provide predictions of when and where carbonate deposits might be found through reservoirs during CO₂ sequestration. Flow experiments through porous media using a supersaturated carbonate fluid were also performed in order to observe flow rates. In order to evaluate precipitation rates and permeability change in the formation, calculated flow rates based on the proposed geochemical clogging model were compared with the experimentally observed data. Both high and low temperature cases were studied to understand how hydrothermal conditions can affect precipitation rates of carbonate. According to chemical kinetics, growth rates of minerals are generally proportional to the saturation index (S.I.) that depends on temperature. Thus, a supersaturated fluid has the advantage of improving the filtration and the amount of C fixation (σ). However, when the ratio of filtration coefficient (λ) to pore fluid velocity (u) increases, the permeability around the injection point tends to be significantly reduced by carbonate accumulation, and thus, this might result in insufficient injection of CO₂. Therefore, it is essential to understand how to control both λ and u so that the precipitation of carbonate can be located as far away from the inlet as possible.     

The influence of carbon source on abiotic organic synthesis and carbon isotope fractionation under hydrothermal conditions

A series of laboratory experiments were performed to investigate the relative contributions of CO and other single-carbon compounds to abiotic synthesis of organic compounds in hydrothermal environments. Experiments were conducted by heating aqueous solutions of CO, CO₂, HCOOH, or CH₄ at 250 °C under reducing conditions, and observing production of CH₄ and other hydrocarbons. Native Fe was included in the experiments as a source of H₂ through reaction with water and as a potential catalyst. Experiments with CO or HCOOH as the carbon source resulted in rapid generation of CH₄ and other hydrocarbons that closely resembled typical products of Fischer-Tropsch organic synthesis. In contrast, experiments using CO₂ or CH₄ as the carbon source yielded no detectable hydrocarbon products. Carbon isotope measurements of reaction products from the CO experiments indicate that the CH₄ and other hydrocarbons were substantially depleted in ¹³C, with CH₄ δ¹³C values 30 to 34‰ lighter than the initial CO. Most of the fractionation apparently occurs during attachment of CO to the catalyst surface and subsequent reduction to surface-bound methylene. The initial step in polymerization of these methylene units to form hydrocarbons involves a small, positive fractionation, so that ethane and ethene are slightly enriched in ¹³C relative to CH₄. However, subsequent addition of carbon molecules to the growing hydrocarbon chain proceeds with no net observable fractionation, so that the isotopic compositions of the C₃₊ light hydrocarbons are controlled by isotopic mass balance. This result is consistent with a previously proposed model for carbon isotopic patterns of light hydrocarbons in natural samples. The abundance and isotopic composition of light hydrocarbons produced with HCOOH as the carbon source were similar to those generated with CO, but the isotopic compositions of non-volatile hydrocarbons diverged, suggesting that the higher hydrocarbons were formed by different mechanisms in the CO and HCOOH experiments. The experiments indicate that CO, and possibly HCOOH, may be critical intermediates in the abiotic formation of organic compounds in geologic environments, and suggest that the low levels of these compounds present in most hydrothermal systems could represent a bottleneck restricting the extent of abiotic organic synthesis in some circumstances.