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1.
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.  相似文献   

2.
The basal plane reactivities of the sheet silicates apophyllite and phlogopite have been studied by hydrothermal atomic force microscopy (HAFM) in situ in aqueous solutions at temperatures from 20 to 140 °C. At pH 4-5.6 (T = 20-100 °C), the apophyllite basal surface undergoes a swelling process which forms square hillocks on the surface. The reaction comprises three sequential morphological transformations that cause swelling to increase from 0.15 to 2.5 nm. In the first two transformations, interlayer cations are replaced by hydronium ions from the solution; the third transformation involves a depolymerization and partial cross-linking of the protonated silicate sheets. The reaction of phlogopite with acidic aqueous solutions (pH 1.5-2) at high temperature (T = 100-140 °C) causes the nucleation of numerous monolayer etch pits on the pristine surface. Where the 2D pits recur at the same lateral position, they can accumulate to a total pit depth of up to 50 nm. The formation of an altered layer has also been detected at these conditions. The alteration affects the uppermost 4-5 layers. The layers are expanded, corrugated, highly unstable, and readily peel off the surface. Etch pit formation has been detected even underneath the altered layer. On the basis of HAFM data, dissolution rates and activation energies were calculated. The presented data show that the basal surface of phlogopite plays an important role in the dissolution process at least at elevated temperatures and that the absolute amount of released material has comparable contributions from both basal surfaces and edge surfaces.  相似文献   

3.
A series of hydrothermal experiments covering a range of temperatures from 175 to 260°C examined the decomposition of formic acid and formate and also investigated the production of formate from reduction of CO2. Decomposition rates measured in this study, which were conducted in gold-TiO2 reactors, were several orders of magnitude slower than those reported in previous studies conducted in steel and Ti-metal reactors, indicating the previous studies substantially overestimated the rate of the reaction owing to reactor catalysis. Although experiments were conducted with several different minerals present (hematite, magnetite, serpentinized olivine, NiFe-alloy), the decomposition rates were similar in each experiment once the effects of fluid pH were accounted for, suggesting that the minerals had no effect on the stability of formic acid or formate. At higher temperatures (>225°C), the rates of both the decomposition of formate and the reduction of CO2 to formate were sufficiently rapid that reactions between dissolved CO2 and formate rapidly attained a state of metastable thermodynamic equilibrium. The results suggest that the amount of formate in many subsurface and hydrothermal fluids is likely to be controlled by equilibrium with dissolved CO2 at the prevailing oxidation state and pH of the fluid. This may account for the high concentrations of formate observed in strongly reducing environments such as serpentinites, as well as the low concentrations relative to other organic acid anions in mildly reducing environments such as oil-filed brines and formation waters in sedimentary basins. Although formate has been suggested to be a reaction intermediate in the formation of abiotic hydrocarbons from reduction of aqueous CO2, production of hydrocarbons was not observed in any of the experiments, except for trace amounts of methane, despite high concentrations of formate and strongly reducing conditions.  相似文献   

4.
Batch reactor experiments were conducted to assess perthitic alkali-feldspar dissolution and secondary mineral formation in an initially acidic fluid (pH = 3.1) at 200 °C and 300 bars. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. Solid reaction products were retrieved from two identical experiments terminated after 5 and 78 days. Scanning electron microscopy revealed dissolution features and significant secondary mineral coverage on feldspar surfaces. Boehmite and kaolinite were identified as secondary minerals by X-ray diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy analysis of alkali-feldspar surfaces before and after reaction showed a trend of increasing Al/Si ratios and decreasing K/Al ratios with reaction progress, consistent with the formation of boehmite and kaolinite.Saturation indices of feldspars and secondary minerals suggest that albite dissolution occurred throughout the experiments, while K-feldspar exceeded saturation after 216 h of reaction. Reactions proceeded slowly and full equilibrium was not achieved, the relatively high temperature of the experiments notwithstanding. Thus, time series observations indicate continuous supersaturation with respect to boehmite and kaolinite, although the extent of this decreased with reaction progress as the driving force for albite dissolution decreased. The first experimental evidence of metastable co-existence of boehmite, kaolinite and alkali feldspar in the feldspar hydrolysis system is consistent with theoretical models of mineral dissolution/precipitation kinetics where the ratio of the secondary mineral precipitation rate constant to the rate constant of feldspar dissolution is well below unity. This has important implications for modeling the time-dependent evolution of feldspar dissolution and secondary mineral formation in natural systems.  相似文献   

5.
Hydrogen sulfide (H2S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 °C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO4 in the presence of variable H2S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H2S occurred under acidic conditions (at pH ∼3-3.5). However, sulfate reduction at pH ∼5.0 was undetectable even at high initial H2S concentrations. To investigate whether the reaction of H2S(aq) and occurs at pH ∼3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO4 and variable H2S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO4 reduction was not measurable in the absence of paraffin even with high H2S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H2S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H2S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc.82, 1911-1916).Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H2S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 °C and a 0.1-°C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H2S pressure. Thus, we propose that the LSC produced from H2S reaction with HC are most likely the reactive intermediates for H2S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content.  相似文献   

6.
We conducted hydrothermal flow-through experiments at 430 °C and 31 MPa to investigate the mechanism of silica precipitation on granite under crustal conditions. Two experiments were performed using different input solutions: a single-component Si solution, and a multi-component solution with minor Al, Na, and K. The degree of supersaturation with respect to quartz, Ω = CSi/CSi,Qtz,eq, where CSi and CSi,Qtz,eq indicate Si concentration in solutions and the solubility of quartz within water, respectively, decreased from 3-3.5 to <1.1 along the flow path. A variety of silica minerals formed during the experiments (opal-A, opal-C, chalcedony, and quartz), and their occurrences and modal abundances changed in response to Ω and the presence of additives in the solution.For near-equilibrium solutions (Ω < ∼1.2), silica precipitation occurred in a simple way in both experiments, being restricted to overgrowths on pre-existing quartz surfaces in the granite. At higher saturation levels (Ω > ∼1.2), silica minerals were deposited on other surfaces in addition to quartz. In the single-component experiment, the dominant silica minerals changed in the order of opal-A → opal-C → quartz with decreasing Si concentration along the flow path. In contrast, in the multi-component experiment, quartz and minor chalcedony formed throughout the entire reaction vessel. This finding indicates that impurities (Na, K, and Al) in the solutions inhibited the precipitation of opal and enhanced the direct nucleation of quartz. The systematic appearance of metastable silica minerals were examined by nucleation processes and macroscopic precipitation kinetics. Our experimental results indicate that different precipitation mechanisms yield contrasting textures, which in turn suggests that vein textures can be used as indicators of solution chemistry within the fracture.  相似文献   

7.
Organic acids and acid anions occur in substantial concentrations in many aqueous geologic fluids and are thought to take part in a variety of geochemical processes ranging from the transport of metals in ore-forming fluids to the formation of natural gas to serving as a metabolic energy source for microbes in subsurface habitats. The widespread occurrence of organic acids and their potential role in diverse geologic processes has led to numerous experimental studies of their thermal stability, yet there remain substantial gaps in our knowledge of the factors that control the rates and reaction pathways for the decomposition of these compounds under geologic conditions. In order to address some of these uncertainties, a series of laboratory experiments were conducted to examine the behavior of organic acids and acid anions under hydrothermal conditions in the presence of minerals. Reported here are results of experiments where aqueous solutions of acetic acid, sodium acetate, or valeric acid (n-pentanoic acid) were heated at 325°C, 350 bars in the presence of the mineral assemblages hematite + magnetite + pyrite, pyrite + pyrrhotite + magnetite, and hematite + magnetite. The results indicate that aqueous acetic acid and acetate decompose by a combination of two reaction pathways: decarboxylation and oxidation. Both reactions are promoted by minerals, with hematite catalyzing the oxidation reaction while magnetite catalyzes decarboxylation. The oxidation reaction is much faster, so that oxidation dominates the decomposition of acetic acid and acetate when hematite is present. In contrast to previous reports that acetate decomposed more slowly than acetic acid, we found that acetate decomposed at slightly faster rates than the acid in the presence of minerals. Although longer-chain monocarboxylic acids are generally thought to decompose by decarboxylation, valeric acid appeared to decompose primarily by “deformylation” to 1-butene plus formic acid. Subsequent decomposition of 1-butene and formic acid generated a variety of short-chain (≤C4) hydrocarbons and moncarboxylic acids as well as CO2. Valeric acid decomposition proceeded more rapidly (by a factor of 2) in the presence of hematite-magnetite-pyrite than with the other mineral assemblages, with the greater reaction rate apparently attributable to the effects of fluid chemistry. Valeric acid was observed to decompose at a substantially faster rate than acetic acid under similar conditions. The results suggest that decomposition of aqueous monocarboxylic acids may make a significant contribution to the conversion of petroleum to light hydrocarbons in natural gas and thermal fluids.  相似文献   

8.
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9.
The Bizielle vein has some unique features among the Pyrenean alpine veins that allow us to address the question of the nature of iron oxides transformations under low temperature hydrothermal conditions, which is well known to prevailed over wide areas of western Europe between early Triassic to early Cretaceous times. Isotopic studies indicate a deep-seated origin of the ore-forming fluids and suggest that the metals were leached from the Variscan basement (mainly from granites). Isotopic geothermometry and regional evidences point to a 250 °C and reducing fluid, being SH2 the predominant S specie. Under such conditions, the proposed in situ deposition of hematite is a consequence of Fe carbonates dissolution and oxidation involving dissolution/precipitation processes in the sense of Putnis. Non-redox model is a quite plausible origin for subsequent hematite to magnetite conversion.  相似文献   

10.
Sandstone dissolution is a common water–rock reaction in the Earth’s crust, but a thorough understanding of this phenomenon is constrained by poorly determined kinetic data. To this end, kinetic data were determined for the dissolution of arkosic sandstone powders in deionised water (pH was about 7.0–7.3 and electrical conductivity was between 0.95 and 1.00 μS/cm). Release rates of dissolved elements were determined over the range 50–350 °C at 20, 15, and 10 MPa using a column flow-through pressure vessel reactor. The conductivity of the outlet solution, measured at room temperature, is dependent on the charge of major cations such as Na+, K+, Ca2+ and Mg2+ at these conditions. The conductivity of the outlet solution was used to determine the steady state of the dissolution of sandstone powders. The pH values of the outlet solutions at the steady state, measured ex situ at room temperature, were about 7.7, 8.3, 8.4, 8.4 and 7.6 at 75, 100, 150, 200 and 250 °C, respectively, at 10 MPa. Silicon, Na, K, Ca, Al and Mg are the major ions found in the solution at low temperatures, but Si is the only major ion retained at higher temperatures (>150 °C). Compared with static experiments, the flowing dissolution experiments occurred at conditions far from equilibrium. The relationship between temperature and dissolution rates of arkosic sandstone powders was described as log R = 0.005469t − 10.50 where R is the dissolution rates of sandstone powders in kg/(m2 s), t is temperature in °C which ranged from 100 to 350 °C at 20 and 15 MPa, and the dissolution rates of sandstone powders were measured only for the major dissolved elements without oxygen in the outlet solutions.  相似文献   

11.
To understand reaction pathways and isotope systematics during mineral-catalyzed abiotic synthesis of hydrocarbons under hydrothermal conditions, experiments involving magnetite and CO2 and H2-bearing aqueous fluids were conducted at 400 °C and 500 bars. A robust technique for sample storage and transfer from experimental apparatus to stable isotope mass spectrometer provides a methodology for integration of both carbon and hydrogen isotope characterization of reactants and products generated during abiogenic synthesis experiments. Experiments were performed with and without pretreatment of magnetite to remove background carbon associated with the mineral catalyst. Prior to experiments, the abundance and carbon isotope composition of all carbon-bearing components were determined. Time-series samples of the fluid from all experiments indicated significant concentrations of dissolved CO and C1-C3 hydrocarbons and relatively large changes in dissolved CO2 and H2 concentrations, consistent with formation of additional hydrocarbon components beyond C3. The existence of relatively high dissolved alkanes in the experiment involving non-pretreated magnetite in particular, suggests a complex catalytic process, likely involving reinforcing effects of mineral-derived carbon with newly synthesized hydrocarbons at the magnetite surface. Similar reactions may be important mechanisms for carbon reduction in chemically complex natural hydrothermal systems. In spite of evidence supporting abiotic hydrocarbon formation in all experiments, an “isotopic reversal” trend was not observed for 13C values of dissolved alkanes with increasing carbon number. This may relate to the specific mechanism of carbon reduction and hydrocarbon chain growth under hydrothermal conditions at elevated temperatures and pressures. Over time, significant 13C depletion in CH4 suggests either depolymerization reactions occurring in addition to synthesis, or reactions between the C1-C3 hydrocarbons and carbon species absorbed on mineral surfaces and in solution.  相似文献   

12.
Stability and solubility of arsenopyrite, FeAsS, in crustal fluids   总被引：3，自引：0，他引：3  
The stability and solubility of natural arsenopyrite (FeAsS) in pure water and moderately acid to slightly basic aqueous solutions buffered or not with H2 and/or H2S were studied at temperatures from 300 to 450°C and pressures from 100 to 1000 bar. The solubilities of FeAsS in pure water and dilute HCl/NaOH solutions without buffering are consistent with the formation of the As(OH)30(aq) species and precipitation of magnetite. At more acid pH (pH ≤2), arsenopyrite dissolves either stoichiometrically or with formation of the As-FeAsS assemblage. In H2S-rich and H2-rich aqueous solutions, arsenopyrite dissolution results in the formation of pyrrhotite (±pyrite) and iron arsenide(s), respectively, which form stable assemblages with arsenopyrite.Arsenic concentrations measured in equilibrium with FeAsS in slightly acid to neutral aqueous solutions with H2 and H2S fugacities buffered by the pyrite-pyrrhotite-magnetite assemblage are 0.0006 ± 0.0002, 0.0055 ± 0.0010, 0.07 ± 0.01, and 0.32 ± 0.03 mol/kg H2O at 300°C/400 bar, 350°C/500 bar, 400°C/500 bar, and 450°C/500 bar, respectively. These values were combined with the available thermodynamic data on As(OH)30(aq) (Pokrovski et al., 1996) to derive the Gibbs free energy of FeAsS at each corresponding temperature and pressure. Extrapolation of these values to 25°C and 1 bar, using the available heat capacity and entropy data for FeAsS (Pashinkin et al., 1989), yields a value of −141.6 ± 6.0 kJ/mol for the standard Gibbs free energy of formation of arsenopyrite. This value implies a higher stability of FeAsS in hydrothermal environments than was widely assumed.Calculations carried out using the new thermodynamic properties of FeAsS demonstrate that this mineral controls As transport and deposition by high-temperature (>∼300°C) crustal fluids during the formation of magmatic-hydrothermal Sn-W-Cu-(Au) deposits. The equilibrium between As-bearing pyrite and the fluid is likely to account for the As concentrations measured in modern high- and moderate-temperature (150 ≤ T ≤ 350°C) hydrothermal systems. Calculations indicate that the local dissolution of arsenopyrite creates more reducing conditions than in the bulk fluid, which is likely to be an effective mechanism for precipitating gold from hydrothermal solutions. This could be a possible explanation for the gold-arsenopyrite association commonly observed in many hydrothermal gold deposits.  相似文献   

13.
The interaction of granitic rock with meteoric fluid is instrumental in determining the chemistry of pore fluids and alteration mineralogy in downflow portions of convective groundwater circulation cells associated with many hydrothermal systems in the continental crust. Hydrothermal experiments and a detailed mineralogical study have been carried out to investigate the hydrothermal alteration of the Carnmenellis Granite, Cornwall, UK. Samples of drill chippings from a borehole 2 km deep in the Carnmenellis Granite have been reacted with a dilute Na-HCO3-Cl fluid in hydrothermal solution equipment at temperatures of 80°, 150° and 250° C and a pressure of 50 MPa, with a water/rock mass ratio of 10, for experiment durations up to 200 days. Fluid samples were analysed for seventeen different chemical components, and solids were examined prior to, and after reaction using SEM, electron microprobe and conventional light optic techniques. Experimental fluids were mildly alkaline (pH 7–8.5) and of low salinity (TDS <800 mgl–1). Mineral-fluid reaction was dominated by the dissolution of plagioclase and the growth of smectite, calcite (at all temperatures), laumontite (at 150° C), wairakite and anhydrite (at 250° C). Final fluids were saturated with respect to quartz and fluorite. Certain trace elements (Li, B, Sr) were either incorporated into solids precipitated during the experiments or sorbed onto mineral surfaces and cannot be considered as conservative (partitioned into the fluid phase) elements. Concentrations of all analysed chemical components showed net increases during the experiments except for Ca (at 250° C) and Mg (at all temperatures). A comparison of the alteration mineralogy observed in the experiments with that present as natural fracture infills in drillcore from the Carnmenellis Granite reveals that the solid products from the experiments correspond closely to mineral assemblages identified as occurring during the later stages of hydrothermal circulation associated with the emplacement of the granite.  相似文献   

14.
Mechanisms of iron oxide transformations in hydrothermal systems   总被引：2，自引：0，他引：2  
Coexistence of magnetite and hematite in hydrothermal systems has often been used to constrain the redox potential of fluids, assuming that the redox equilibrium is attained among all minerals and aqueous species. However, as temperature decreases, disequilibrium mineral assemblages may occur due to the slow kinetics of reaction involving the minerals and fluids. In this study, we conducted a series of experiments in which hematite or magnetite was reacted with an acidic solution under H2-rich hydrothermal conditions (T = 100-250 °C, ) to investigate the kinetics of redox and non-redox transformations between hematite and magnetite, and the mechanisms of iron oxide transformation under hydrothermal conditions. The formation of euhedral crystals of hematite in 150 and 200 °C experiments, in which magnetite was used as the starting material, indicates that non-redox transformation of magnetite to hematite occurred within 24 h. The chemical composition of the experimental solutions was controlled by the non-redox transformation between magnetite and hematite throughout the experiments. While solution compositions were controlled by the non-redox transformation in the first 3 days in a 250 °C experiment, reductive dissolution of magnetite became important after 5 days and affected the solution chemistry. At 100 °C, the presence of maghemite was indicated in the first 7 days. Based on these results, equilibrium constants of non-redox transformation between magnetite and hematite and those of non-redox transformation between magnetite and maghemite were calculated. Our results suggest that the redox transformation of hematite to magnetite occurs in the following steps: (1) reductive dissolution of hematite to and (2) non-redox transformation of hematite and to magnetite.  相似文献   

15.
The volatilization kinetics of single crystal α-SiC, polycrystalline β-SiC, and SiO2 (cristobalite or glass) were determined in H2-CO2, CO-CO2, and H2-CO-CO2 gas mixtures at oxygen fugacities between 1 log unit above and 10 log units below the iron-wüstite (IW) buffer and temperatures in the range 1151 to 1501°C. Detailed sets of experiments on SiC were conducted at 2.8 and 6.0 log units below IW (IW-2.8 and IW-6.0) at a variety of temperatures, and at 1300°C at a variety of oxygen fugacities. Transmission electron microscopic and Rutherford backscattering spectroscopic characterization of run products shows that the surface of SiC exposed to IW-2.8 is characterized by a thin (<1 μm thick), continuous layer of cristobalite. SiC exposed to IW-6.0 lacks such a layer (or its thickness is <0.01 μm), although some SiO2 was found within pits and along incised grain boundaries.In H2-CO2 gas mixtures above ∼IW-3, the similarity of the SiC volatilization rate and of its dependence on temperature and fO2 to that for SiO2 suggests that SiC volatilization is controlled by volatilization of a SiO2 layer that forms on the surface of the SiC. With decreasing log fO2 from ∼IW-3 to ∼IW-6, the SiC volatilization rate is constant at constant temperature, whereas that for SiO2 increases. The independence of the SiC volatilization rate from the gas composition under these conditions suggests that the rate-controlling step is a solid-solid reaction at the internal SiC/SiO2 interface. For gas compositions more reducing than ∼IW-6, the SiC volatilization rate increases with decreasing fO2, with both bare SiC surfaces and perhaps silica residing in pits and along incised grain boundaries contributing to the overall reaction rate.If the volatilization mechanism and reaction rate in the solar nebula were the same as in our H2-CO2 experiments at IW-6.0, then estimated lifetimes of 1-μm-diameter presolar SiC grains range from several thousand years at ∼900°C, to ∼1 yr at 1100°C, ∼1 d at 1300°C, and ∼1 h at 1400°C. The corresponding lifetimes for 10-μm SiC grains would be an order of magnitude longer. If the supply of oxidants to surfaces of presolar SiC grains were rate limiting—for example, at T > 1100°C for Ptot= 10−6 atm and sticking coefficient = 0.01, then the calculated lifetimes would be about 10 yr for 10-μm-diameter grains, essentially independent of temperature. The results thus imply that presolar SiC grains would survive short heating events associated with formation of chondrules (minutes) and calcium-, aluminum-rich inclusions (days), but would have been destroyed by exposure to hot (≥900°C) nebular gases in less than several thousand years unless they were coated with minerals inert to reaction with a nebular gas.  相似文献   

16.
The reaction stilbite=laumontite+3 quartz+3 H2O was experimentally studied using conventional hydrothermal techniques employing mineral mixtures consisting of reactants and products in 91 and 19 ratios. Equilibrium was demonstrated; the univariant curve passes through about 170° C and 2000 bars, 185°±10° C and 3000 bars, about 185° C and 4000 bars, and 183°±10° C at 5000 bars P fluid. These results combined with published equilibria for analcime, laumontite, wairakite and prehnite permit delineation of the P-T conditions for the zeolite and prehnite-pumpellyite facies metamorphism in the Tanzawa Mountains, Japan.  相似文献   

17.
The abiotic polymerization of amino acids may have been important for the origin of life, as peptides may have been components of the first self-replicating systems. Though amino acid concentrations in the primitive oceans may have been too dilute for significant oligomerization to occur, mineral surface adsorption may have provided a concentration mechanism. As unactivated amino acid polymerization is thermodynamically unfavorable and kinetically slow in aqueous solution, we studied mainly the reverse reaction of polymer degradation to measure the impact of mineral surface catalysis on peptide bonds.Aqueous glycine (G), diglycine (GG), diketopiperazine (DKP), and triglycine (GGG) were reacted with minerals (calcite, hematite, montmorillonite, pyrite, rutile, or amorphous silica) in the presence of 0.05 M, pH 8.1, KHCO3 buffer and 0.1 M NaCl as background electrolyte in a thermostatted oven at 25, 50 or 70 °C. Below 70 °C, reaction kinetics were too sluggish to detect catalytic activity over amenable laboratory time-scales. Minerals were not found to have measurable effects on the degradation or elongation of G, GG or DKP at 70 °C in solution. At 70 °C pyrite was the most catalytic mineral with detectible effects on the degradation of GGG, although several others also displayed catalytic behavior. GGG degraded ∼1.5-4 times faster in the presence of pyrite than in control reactions, depending on the ratio of solution concentration to mineral surface area. The rate of pyrite catalysis of GGG hydrolysis was found to be saturable, suggesting the presence of discrete catalytic sites on the mineral surface. The mineral-catalyzed degradation of GGG appears to occur via a GGG → DKP + G mechanism, rather than via GGG → GG + G, as in solution-phase reactions. These results are compatible with many previous findings and suggest that minerals may have assisted in peptide synthesis in certain geological settings, specifically by speeding the approach to equilibrium in environments where amino acids were already highly concentrated, but that minerals may not significantly alter the expected solution-phase equilibria. Thus the abiotic synthesis of long peptides may have required activating agents, dry heating at higher temperatures, or some form of phase separation.  相似文献   

18.
We present results of incubation studies conducted at low temperatures (∼4°C) in the vicinity of a seafloor hydrothermal vent system. We reacted Fe-, S-, Cu-, and Zn-bearing minerals including pyrite, marcasite, chalcopyrite, sphalerite, elemental sulfur, and a portion of a natural chimney sulfide structure for 2 months at the Main Endeavour Segment of the Juan de Fuca Ridge in the Pacific Ocean. Our study utilizes Fluorescent In Situ Hybridizations (FISH), Scanning and Transmission Electron Microscopy (SEM, TEM), and light microscopic analysis. The surfaces of these minerals are solely colonized by Bacteria and not by Archaea. Colonization densities vary over an order of magnitude with the following sequence: elemental sulfur > chimney sulfide > marcasite > pyrite > sphalerite > chalcopyrite, and correspond well with the abiotic oxidation kinetics of these materials, excepting elemental sulfur, which is both the least reactive to oxidizing species and the most heavily colonized. Colonization densities also correspond with apparent degree of reaction (dissolution pitting + accumulation of secondary alteration products). Heavy accumulations of secondary Fe oxides on Fe-bearing minerals, most notably on the chimney sulfide, form in situ as the result of mineral dissolution and the activity of neutrophilic Fe-oxidizing bacteria. Results suggest that mineral-oxidizing bacteria play a prominent role in weathering of seafloor sulfide deposits, and that microbial utilization of mineral substrates contributes to biomass production in seafloor hydrothermal environments.  相似文献   

19.
Two experiments using cylindrical samples of a dolomite-quartz rock were carried out in a conventional hydrothermal apparatus for the forward reaction: 1 dolomite + 2 quartz = 1 diopside + 2 CO2, in order to compare the mechanism and the kinetics with results from experiments using mineral powders of dolomite and quartz at the same P-T-X conditions. Experimental conditions were as follows: total pressure 500 MPa; temperature 680° C (overstepping 65° C); CO2 content of the fluid phase, consisting of carbon dioxide and water, was nearly 90 mol%; the fluid/rock ratio was 1:37, and the H2O/rock ratio was about 1:740; run duration was 92 days. Scanning electron microscope (SEM) examination of a polished axial section of the rock cylinders after the run, using back-scattered electrons (BSE), shows that the reaction produced corona textures. The diopside crystals nucleate and grow exclusively on dolomite surfaces adjacent to quartz grains, i.e. in regions where there is intimate contact between the reactants. The dolomite matrix, in contrast, is diopside free. A concept of microsystems is used to compare directly the rock cylinder results with those from runs done with mineral powders. The microsystems, which consist of quartz, dolomite and diopside, are connected by the intergranular space which is filled by the fluid phase. The SEM analysis of the rock cylinders indicates a dissolution-crystallization mechanism operating in the microsystems; this is consistent with the results of experiments using dolomite quartz powders (Lüttge et al. 1989). It can be demonstrated that reaction kinetics in mineral powder runs are interface controlled as long as the newly formed diopside crystals do not cover the dolomite surfaces completely (Lüttge and Metz 1991 c). This result is applicable to each microsystem of the rock cylinder, since the reaction mechanism and the resulting textures are the same in both kinds of experiments. The reaction is much slower outside the microsystems, i.e. in the dolomite matrix but in the close vicinity of the quartz grains. At these places, the reaction is controlled by the transport of Si-species in the CO2-rich fluid phase filling the intergranular space. The reaction is absent in quartz-free regions of the dolomite matrix. Calculations and measurements of the extent of reaction progress in both kinds of experiments give results of the same order of magnitude: the conversion, and therefore the reaction rate, differs by less than a factor of two. The conclusion is that there are no differences, in principle, concerning mechanisms, rate controls, rates, and resulting textures between rock cylinder experiments, and mineral powder experiments.  相似文献   

20.
Experimental investigation was made on hydrothermal alteration of sericite in acid solution. It is found that the sericite is changed to pyrophyllite through kaolinite at 270° C and 260° C, and the alteration is considered to be a consecutive reaction involving two steps, from sericite to kaolinite and from kaolinite to pyrophyllite. On the other hand, pyrophyllite is not formed at 190° C and the sericite is altered to kaolinite. The rate of reaction in each step of this hydrothermal alteration is dependent on reaction temperature and chemical composition of the solution. From the results of the quantitative analyses of the experimental products, kinetic constants and related parameters were obtained.By using these numerical values, an alteration process can be followed in a given model. Computed results for some cases of an alteration of sericite in acid solution are presented. Geological phenomena such as rock alteration or weathering are thought to progress in a disequilibrium state and in an open system. An attempt described in this paper is a physicochemical approach to treat an alteration process accompanied with material transfer occurring in an open system from a kientic viewpoint.  相似文献   

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