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1.
《Applied Geochemistry》1996,11(4):511-521
It is difficult to measure accurately the natural long-term corrosion rates of highly durable nuclear waste glasses. Care should be taken when using data from high temperature experiments to predict corrosion rates under ambient repository conditions as there are many factors (such as the precipitation of secondary compounds, the chemistry of the water in contact with the glass, or circulation of this water through the repository) that can influence the temperature dependence of aqueous reactions. In this study, some standard leach tests using pure water, in continuous flow and direct sampling autoclaves, were performed on a synthetic medieval glass. Archaeological glass samples of a similar composition and which had suffered several centuries of corrosion in damp soil had been the subject of previous studies. The corrosion of the archaeological samples in damp soil was well understood and the aim was to determine how well standard leach tests would predict the observed corrosion.The experimentally measured long-term corrosion rates were not simply dependent on temperature, therefore they could not be used to predict either the corrosion rates or products found on the archaeological samples. In continuous flow experiments this was largely because the release of some cations (e.g. Mg2+) was proportional to the flow rates used, and so the long-term corrosion was dependent on both flow rate and temperature. In the autoclave experiments, concentrations of dissolved ions climbed rapidly in the small water volume, leading to the precipitation of complex mineral phase assemblages. The experiments did not reach silica saturation, therefore the long-term rates measured were a function of both the temperature and the extent of reaction. The initial release rates of silica and of the network modifying cations showed an Arrhenius temperature dependence with an activation energy of about 78.5 kJmol−1. These results would have predicted the soil corrosion of the archaeological samples to within about 30%, i.e. the initial corrosion rate in pure water was similar to the long-term rate in damp soil. As an explanation of the experimental observations it is suggested that clay minerals in the soil consumed silica as the glass dissolved, maintaining under-saturated conditions and allowing corrosion at a rate similar to the initial rate in pure water.  相似文献   

2.
We derive a compositional compressible two-phase, liquid and gas, flow model for numerical simulations of hydrogen migration in deep geological repository for radioactive waste. This model includes capillary effects and the gas high diffusivity. Moreover, it is written in variables (total hydrogen mass density and liquid pressure) chosen in order to be consistent with gas appearance or disappearance. We discuss the well possedness of this model and give some computational evidences of its adequacy to simulate gas generation in a water-saturated repository.  相似文献   

3.
Hydrogen gas produced in the subsurface from the hydration of mafic rocks is known to be a major energy source for chemolithotrophic life in extreme environments such as hydrothermal vents. The possibility that in situ anaerobic microorganisms present in the deep subsurface are sustained by low temperature H2-generating water–rock reactions taking place around them is being investigated. Whether the growth and activity of H2-utilizing microbes directly influences aqueous geochemistry, rates of mineral dissolution, and the chemical composition of the alteration products is also being quantitatively evaluated.To explore how microorganisms are affected by water–rock reactions, and how their activity may in turn affect reaction progress, laboratory experiments have been conducted to monitor the growth of a methanogenic Archaea in the presence of H2(g) produced from low temperature water–Fe0–basalt reactions. In these systems, the conversion of Fe(II) to Fe(III) and subsequent hydrolysis of water is responsible for the production of H2(g). To characterize key components of the geochemical system, time series measurements of H2 and CH4 gas concentrations, Fe and Si aqueous concentrations, and spatially resolved synchrotron-based analyses of microscale Fe distribution and speciation were conducted. Culture experiments were compared with an abiotic control to document changes in the geochemistry both in the presence and absence of the methanogen.In the control abiotic batch experiment, H2 was continuously produced, until the headspace became saturated, while in the biotic experiments, microbial consumption of H2 for methanogenesis draws H2 down and produces CH4. Purging the headspace gas reinitiates H2 and CH4 production in abiotic and culture experiments, respectively. Mass balance analysis of the amount of CH4 produced suggests that the total H2 production in microbial experiments does not exceed the abiotic experiment. Soluble Si concentrations, while buffered to relatively constant values, were higher in culture experiments than the abiotic control.Iron(aq) concentrations appear to respond to perturbations of H2 and CH4 gas concentrations in both culture experiments and the abiotic control. A pulse of Fe preceded the rise in either H2 or CH4 production, and as the gas concentrations increased the Fe(aq) decreased. Iron-bearing mineral assemblages change with increasing reaction time and mineral assemblages vary between culture experiments and the abiotic control. These geochemical trends suggest that there are different reaction paths between the culture experiments and the abiotic control.The hydration of mafic rocks is a common geologic reaction and one that has taken place on Earth for the majority of its history and is postulated to occur on Mars. These reactions are important because of their effect on the rheology and geochemistry of the ocean crust. While most often studied at temperatures of ～250 °C, this work suggests that at lower temperatures microorganisms may have a profound effect on what has long been thought to be solely an abiotic reaction, and may produce diagnostic mineral assemblages that will be preserved in the geological record.  相似文献   

4.
Here we present a long-term nonisothermal reactive transport model for the interactions of the corrosion products of a carbon-steel canister and the compacted bentonite of the engineered barrier of a high-level radioactive waste repository in granite. Canister corrosion causes an increase in the pH and the concentration of dissolved Fe2+ of the bentonite porewater. Iron precipitates as magnetite and siderite and sorbs via cation exchange and surface complexation on weak sites. Magnetite precipitation reduces significantly the porosity of the bentonite near the canister. The thickness of the zone of reduced porosity is 7 cm at t = 1 Ma. This thickness increases significantly when the dependence of the corrosion rate on the chemical conditions is considered and decreases 3 cm when smectite dissolution and analcime precipitation are taken into account. Model results are not significantly sensitive to the thermal transient and the effect of temperature on the corrosion rate. The conclusions of our simulations are consistent for the most part with those reported by others for engineered barrier systems at similar chemical conditions.  相似文献   

5.
Hydrogen gas (H2) may be produced by the anoxic corrosion of steel components in underground structures, such as geological repositories for radioactive waste. In such environments, hydrogen was shown to serve as an electron donor for autotrophic bacteria. High gas overpressures are to be avoided in radioactive waste repositories and, thus, microbial consumption of H2 is generally viewed as beneficial. However, to fully consider this biological process in models of repository evolution over time, it is crucial to determine the in situ rates of microbial hydrogen oxidation and sulfate reduction. These rates were estimated through two distinct in situ experiments, using several measurement and calculation methods. Volumetric consumption rates were calculated to be between 1.13 and 1.93 μmol cm−3 day−1 for H2, and 0.14 and 0.20 μmol cm−3 day−1 for sulfate. Based on the stoichiometry of the reaction, there is an excess of H2 consumed, suggesting that it serves as an electron donor to reduce electron acceptors other than sulfate, and/or that some H2 is lost via diffusion. These rate estimates are critical to evaluate whether biological H2 consumption can negate H2 production in repositories, and to determine whether sulfate reduction can consume sulfate faster than it is replenished by diffusion, which could lead to methanogenic conditions.  相似文献   

6.
Release of long-lived radionuclides such as plutonium and caesium from spent nuclear fuel in deep geological repositories will depend mainly on the dissolution rate of the UO2 fuel matrix. This dissolution rate will, in turn, depend on the redox conditions at the fuel surface. Under oxidative conditions UO2 will be oxidised to the 1000 times more soluble UO2.67. This may occur in a repository as the reducing deep groundwater becomes locally oxidative at the fuel surface under the effect of α-radiolysis, the process by which α-particles emitted from the fuel split water molecules. On the other hand, the groundwater corrodes canister iron generating large amounts of hydrogen. The role of molecular hydrogen as reductant in a deep bedrock repository is questioned. Here we show evidence of a surface-catalysed reaction, taking place in the H2-UO2-H2O system where molecular hydrogen is able to reduce oxidants originating from α-radiolysis. In our experiment the UO2 surface remained stoichiometric proving that the expected oxidation of UO2.00 to UO2.67 due to radiolytic oxidants was absent. As a consequence, the dissolution of UO2 stopped when equilibrium was reached between the solid phase and U4+ species in the aqueous phase. The steady-state concentration of uranium in solution was determined to be 9 × 10−12 M, about 30 times lower than previously reported for reducing conditions. Our findings show that fuel dissolution is suppressed by H2. Consequently, radiotoxic nuclides in spent nuclear fuel will remain immobilised in the UO2 matrix. A mechanism for the surface-catalysed reaction between molecular hydrogen and radiolytic oxidants is proposed.  相似文献   

7.
Thermodynamic and Kinetic Properties of Natural Brines   总被引：4，自引：0，他引：4  
The physical chemistry of natural brines made up of mostly NaCl has been studied over the years. In this article, the work on the thermodynamics and kinetics of processes in NaCl brines will be examined. The importance of ionic interactions of the processes will be stressed. This will include the pressure–volume–temperature and physical–chemical properties of NaCl and other brine salts from 0 to 6 m, 0 to 200°C, and 0 to 1,000 bar applied pressures. Acid–base, gas–liquid, solid–liquid, and ion–complex formation processes in NaCl are examined. Equations that can be used to estimate the equilibria in NaCl are given. Pitzer models are discussed that can be used to estimate ionic equilibria in brines. The oxidation of Fe(II) and Cu(I) with O2 and H2O2 and the reduction of Cu(II) with H2O2 in NaCl are examined in terms of ionic complexes of metals with OH? and CO3 2?. The oxidation of H2S with O2 and H2O2 is also examined in NaCl media. Equations are given that can be used to estimate the effect of ionic interactions on kinetic processes in NaCl.  相似文献   

8.
Highly reducing and high-pH vent fluids characterize moderately low temperature ultramafic-hosted hydrothermal systems, such as the recently discovered Lost City hydrothermal field at 30°N Mid-Atlantic Ridge Ridge (MAR). To better understand the role of mineral reaction rates on changes in fluid chemistry and mineralization processes in these and similar systems, we conducted an experimental study involving seawater and peridotite at 200 °C, 500 bar. Time series changes in fluid chemistry were monitored and compared with analogous data predicted using experimental and theoretical data for mineral dissolution rates. Although there was qualitative agreement between predicted and measured changes in the chemical evolution of the fluid for some species, the rate and magnitude of increase in pH, dissolved chloride and H2 did not agree well with predictions based on theoretical modeling results. Experimental data indicate that dissolved H2 abruptly and intermittently increased, reaching a value only approximately 20% of that predicted assuming magnetite as the primary Fe-bearing alteration phase. The distribution and valence of Fe in primary and secondary minerals reveal that the most abundant secondary mineral, serpentine, contained significant amounts of both ferric and ferrous Fe, with the less abundant brucite, also being Fe-rich (XFe = 0.3). Surprisingly, magnetite was present in only trace amounts, indicating that H2 generation was largely accommodated by the formation of Fe-chrysotile. Accordingly, the diversity of Fe-bearing secondary minerals together with rates of serpentinization less than theoretically predicted, account best for the relatively low dissolved H2 concentrations produced. Thus, the experimental data can be used to obtain provisional estimates of thermodynamic data for Fe-bearing minerals, enhancing the application of reaction path models depicting mass transfer processes during serpentinization at mid-ocean ridges. Similarly, the observed differences between theoretically predicted and experimentally measured pH values result from constraints imposed by complex patterns of mass transfer inherent to the experimental system. In particular, the experimental observation of a late stage increase in Na/Cl ratio likely results from the dissolution of a Na2O component of clinopyroxene, which causes pH to increase sufficiently to induce precipitation of a Ca-bearing phase, perhaps portlandite. As with the redox variability observed during the experiment, this event could not be predicted, underscoring the need to use caution when modeling alteration processes in the chemically complex ultramafic-hosted hydrothermal systems at elevated temperatures and pressures.  相似文献   

9.
In recent years, serpentinized ultramafic rocks have received considerable attention as a source of H2 for hydrogen-based microbial communities and as a potential environment for the abiotic synthesis of methane and other hydrocarbons within the Earth’s crust. Both of these processes rely on the development of strongly reducing conditions and the generation of H2 during serpentinization, which principally results from reaction of water with ferrous iron-rich minerals contained in ultramafic rocks. In this report, numerical models are used to investigate the potential influence of chemical thermodynamics on H2 production during serpentinization. The results suggest that thermodynamic constraints on mineral stability and on the distribution of Fe among mineral alteration products as a function of temperature are likely to be major factors controlling the extent of H2 production. At high temperatures (>∼315 °C), rates of serpentinization reactions are fast, but H2 concentrations may be limited by the attainment of stable thermodynamic equilibrium between olivine and the aqueous fluid. Conversely, at temperatures below ∼150 °C, H2 generation is severely limited both by slow reaction kinetics and partitioning of Fe(II) into brucite. At 35 MPa, peak temperatures for H2 production occur at 200-315 °C, indicating that the most strongly reducing conditions will be attained during alteration within this temperature range. Fluids interacting with peridotite in this temperature range are likely to be the most productive sources of H2 for biology, and should also produce the most favorable environments for abiotic organic synthesis. The results also suggest that thermodynamic constraints on Fe distribution among mineral alteration products have significant implications for the timing of magnetization of the ocean crust, and for the occurrence of native metal alloys and other trace minerals during serpentinization.  相似文献   

10.
This paper reviews various coal seam gas (CSG) models that have been developed for the Sydney Basin, and provides an alternative interpretation for gas composition layering and deep-seated CO2 origins. Open file CSG wells, supplemented by mine-scale information, were used to examine trends in gas content and composition at locations from the margin to the centre of the basin. Regionally available hydrochemistry data and interpretations of hydrodynamics were incorporated with conventional petroleum well data on porosity and permeability. The synthesised gas and groundwater model presented in this paper suggests that meteoric water flow under hydrostatic pressure transports methanogenic consortia into the subsurface and that water chemistry evolves during migration from calcium-rich freshwaters in inland recharge areas towards sodium-rich brackish water down-gradient and with depth. Groundwater chemistry changes result in the dissolution and precipitation of minerals as well as affecting the behaviour of dissolved gases such as CO2. Mixing of carbonate-rich waters with waters of significantly different chemistries at depth causes the liberation of CO2 gas from the solution that is adsorbed into the coal matrix in hydrodynamically closed terrains. In more open systems, excess CO2 in the groundwater (carried as bicarbonate) may lead to precipitation of calcite in the host strata. As a result, areas in the central and eastern parts of the basin do not host spatially extensive CO2 gas accumulations but experience more widespread calcite mineralisation, with gas compositions dominated by hydrocarbons, including wet gases. Basin boundary areas (commonly topographic and/or structural highs) in the northern, western and southern parts of the basin commonly contain CO2-rich gases at depth. This deep-seated CO2-rich gas is generally thought to derive from local to continental scale magmatic intrusions, but could also be the product of carbonate dissolution or acetate fermentation.  相似文献   

11.
张水昌  朱光有  何坤 《岩石学报》2011,27(3):809-826
硫酸盐热化学还原作用(Thermochemical sulfate reduction, TSR)是发生在油气藏中复杂的有机-无机相互作用,它不仅会引起含H2S天然气的富集,其产生的酸性气体对碳酸盐岩储层还具有明显的溶蚀改造作用。本文基于黄金管热模拟实验,研究了TSR反应对原油裂解气的生成的影响,发现这种氧化还原反应的存在能明显降低原油的稳定性,促进具高干燥系数的含H2S天然气的生成。结合原位激光拉曼实验结果,证实了实际油藏中启动TSR反应的最可行的氧化剂应该是硫酸盐接触离子对(CIP)。全面探讨了影响TSR反应的地质和地球化学因素,提出除了初始原油的组分特征、不稳定含硫化合物(LSC)的含量外,地层水的含盐类型及盐度同样是控制TSR反应的关键因素。同时,基于大量地质分析,发现TSR对碳酸盐岩储层具有明显的溶蚀改造作用。结合溶蚀模拟实验,提出了酸性流体对碳酸盐储层溶蚀改造的机制,且深层碳酸盐岩层存在一个由TSR作用形成的次生孔隙发育带。研究认为,烃类与硫酸盐矿物的氧化还原反应与其产物对碳酸盐岩储层的改造是TSR作用的两个不可分割的部分,它们相互依存和制约。  相似文献   

12.
Final disposal of high-level radioactive waste in deep repositories in clay formations is being considered by several countries. Repository safety assessment requires the use of numerical models of groundwater flow, solute transport and chemical processes. These models are being developed from data and knowledge gained from in situ experiments such as the CERBERUS experiment carried out at the HADES facility excavated in the Boom clay formation at Mol (Belgium). This long-term experiment is aimed at evaluating the effect of heating and radiation in Boom clay. The test was performed in a cased well drilled at 223 m depth and lasted from 1989 to 1994. A 60Co source of 400 TBq and two heaters were emplaced inside the well. Dose rate, temperature, porewater pressure and pH/Eh were measured in situ during the experiment and gas and porewater samples were taken for chemical analyses. Here a coupled thermo-hydro-geochemical (THC) model of the CERBERUS experiment is presented which accounts simultaneously for heating, radiation, solute diffusion and a suite of geochemical reactions including: aqueous complexation, acid–base, redox, mineral dissolution/precipitation, cation exchange and gas dissolution/ex-solution. Computed results indicate that heating and radiation causes a slight oxidation, a decrease in pH, slight changes in porewater chemistry and pyrite dissolution near the well. THC model results follow the general evolution of chemical data, but cannot fit SO4 data. Model discrepancies are partly overcome when microbially-mediated Fe and SO4 reduction are taken into account in a coupled thermo-hydro-bio-geochemical (THBC) model. This THBC model captures the trends of geochemical data, improves the fit to dissolved SO4 and predicts pyrite precipitation, a process observed near the CERBERUS well. The ability of the THBC numerical model to reproduce the overall trends of geochemical data of the CERBERUS experiment provides confidence in such a model as a suitable tool for the long-term prediction of geochemistry in the near field of a HLW repository in clay. However, the small number of available chemical data throughout the experiment and the lack of DOC and microbial data allow only a partial validation of the THBC model.  相似文献   

13.
Cheng  Wei  Chen  Ren-peng  Hong  Peng-yun  Cui  Yu-jun  Pereira  Jean-Michel 《Acta Geotechnica》2020,15(10):2741-2755

In thermal-related engineering such as thermal energy structures and nuclear waste disposal, it is essential to well understand volume change and excess pore water pressure buildup of soils under thermal cycles. However, most existing thermo-mechanical models can merely simulate one heating–cooling cycle and fail in capturing accumulation phenomenon due to multiple thermal cycles. In this study, a two-surface elasto-plastic model considering thermal cyclic behavior is proposed. This model is based on the bounding surface plasticity and progressive plasticity by introducing two yield surfaces and two loading yield limits. A dependency law is proposed by linking two loading yield limits with a thermal accumulation parameter nc, allowing the thermal cyclic behavior to be taken into account. Parameter nc controls the evolution rate of the inner loading yield limit approaching the loading yield limit following a thermal loading path. By extending the thermo-hydro-mechanical equations into the elastic–plastic state, the excess pore water pressure buildup of soil due to thermal cycles is also accounted. Then, thermal cycle tests on four fine-grained soils (natural Boom clay, Geneva clay, Bonny silt, and reconstituted Pontida clay) under different OCRs and stresses are simulated and compared. The results show that the proposed model can well describe both strain accumulation phenomenon and excess pore water pressure buildup of fine-grained soils under the effect of thermal cycles.

  相似文献   

14.
Mineral aerosols play a significant role in gas–solid interfacial and atmospheric chemistry. Carbonation of olivine aerosol, which takes place in a multiphase reaction processes, can be an effective means to reduce the concentration of atmospheric carbon dioxide. Due to the presence of a huge reserve of silicate minerals in nature, olivine aerosol could be an ideal potential raw material for mineral carbonation for its higher reactivity with H2O and CO2. However, quantitative information about the carbonation process on the surface of natural olivine aerosol is not available. In this paper, calculations on the carbonation reaction processes with and without a H2O molecule using a periodic olivine model has been carried out via the density functional theory. The pathways and their corresponding energies and structures in the carbonation reactions have been established, and the effect of water as means to reduce the energy barriers and stabilize the carbonated structures by forming hydrogen bonds has been confirmed.  相似文献   

15.
The candidate repository for high-level nuclear waste in the Gorleben salt dome, Germany, is expected to host 8,550 tonnes of uranium in burnt fuel. It has been proposed that 5,440 waste containers be deposited at a depth of about 800?m. There is 260?C280?m of siliciclastic cover sediments above the proposed repository. The potential groundwater contamination in the siliciclastic aquifer is simulated with the TOUGHREACT and TOUGH2-MP codes for a three-dimensional model with 290,435 elements. Two deterministic cases are simulated. The single-phase case considers the transport of radionuclides in the liquid phase only. The two-phase case accounts for hydrogen gas generated by the corrosion of waste containers and release of gaseous C-14. The gas release via a backfilled shaft is assumed to be steady (non-explosive). The simulation period is 2,000,000 years for the single-phase case and 7,000 years for the two-phase case. Only the radioactive dose in the two-phase case is higher than the regulatory limit (0.1?mSv/a).  相似文献   

16.
针对在山西晋城赵庄煤矿井下测定瓦斯解吸压力先升高后降低的异常情况,通过对仪器设备和现场环境存在的原因进行排查分析,确定是由于瓦斯解吸过程中吸热导致的罐内气体温度降低,从而出现解吸压力的测定结果异常。为了解决该问题,利用良好导热材料设计加工成煤样罐,使罐内外达到热平衡,分别研究煤样罐置于空气和水介质中的解吸压力,实验发现煤样罐放置空气中出现了先升高后降低的现象,而在水中解吸压力快速回升。依据实验室瓦斯恒温解吸装置的水浴原理,设计加工形成了双壁内充填水的煤样罐,定量研究分析了煤样甲烷气体解吸热、比热容及需水量,通过实验室测定分析赵庄煤矿煤样的瓦斯解吸规律,验证了该煤样罐能够满足工业应用要求。   相似文献   

17.
Boom Clay is studied as a potential host formation for the disposal of high-and intermediate level long-lived radioactive waste in Belgium. In such a geological repository, generation of gases (mainly H2 from anaerobic corrosion) will be unavoidable. In order to make a good evaluation of the balance between gas generation vs. gas dissipation for a particular waste form and/or disposal concept, good estimates for gas diffusion coefficients of dissolved gases are essential. In order to obtain an accurate diffusion coefficient for dissolved hydrogen in saturated Boom Clay, diffusion experiments were performed with a recently developed through-diffusion set-up for dissolved gases. Due to microbial activity in the test set-up, conversion of hydrogen into methane was observed within several experiments. A complex sterilisation procedure was therefore developed in order to eliminate microbiological disturbances. Only by a combination of heat sterilisation, gamma irradiation and the use of a microbial inhibitor, reliable, reproducible and accurate H2(g) diffusion coefficients (measured at 21 °C) for samples oriented parallel (Deff = 7.25 × 10−10 m2/s and Deff = 5.51 × 10−10 m2/s) and perpendicular (Deff = 2.64 × 10−10 m2/s) to the bedding plane were obtained.  相似文献   

18.
We studied the oxidation-sulfidation behavior of an Fe-based alloy containing 4.75 wt.% Ni, 0.99 wt.% Co, 0.89 wt.% Cr, and 0.66 wt.% P in H2-H2O-CO-CO2-H2S gas mixtures at 1000 °C. The samples were cooled at rates of ∼3000 °C/h, comparable to estimates of the conditions after a chondrule-formation event in the early Solar System. Gas compositions were monitored in real time by a quadrupole mass spectrometer residual gas analyzer. Linear rate constants associated with gas-phase adsorption were determined. Reaction products were analyzed by optical microscopy, wavelength-dispersive-spectroscopy X-ray elemental mapping, and electron probe microanalysis. Based on analysis of the Fe-Ni-S ternary phase diagram and the reaction products, the primary corrosion product is a liquid of composition 66.6 wt.% Fe, 3.5 wt.% Ni, 29.9 wt.% S, and minor amounts of P, Cr, and Co. Chromite (FeCr2O4) inclusions formed by oxidation and are present in the metal foil and at the outer boundary between the sulfide and experimental atmosphere. During cooling the liquid initially crystallizes into taenite (average composition ∼15 wt.% Ni), monosulfide solid solution [mss, (Fe,Ni,Co,Cr)1−xS], and Fe-phosphates. Upon further cooling, kamacite exsolves from this metal, enriching the taenite in Ni. The remnant metal core is enriched in P and Co and depleted in Cr at the reaction interface, relative to the starting composition. The unreacted metal core composition remains unchanged, suggesting the reactions did not reach equilibrium. We present a detailed model of reaction mechanisms based on the observed kinetics and sample morphologies, and discuss meteoritic analogs in the CR chondrite MacAlpine Hills 87320.  相似文献   

19.
A four month study of a man-made lake used for hydroelectric power generation in northeastern Pennsylvania USA was conducted to investigate seasonal anoxia and the effects of sulfide species being transported downstream of the power generation equipment. Water column analyses show that the system is iron-rich compared to sulfide. Total Fe(II) concentrations in the hypolimnion are typically at least twice the total sulfide levels. In situ voltammetric analyses show that free Fe(II) as [Fe(H2O)6]2+ or free H2S as H2S/HS- are either not present or at trace levels and that iron-rich sulfide complexes are present. From the in situ data and total Fe(II) and H2S measurements, we infer that these iron-rich sulfide complexes may have stoichiometries such as Fe2SH3+ (or polymeric forms of this and other stoichiometries). These iron-rich sulfide complexes appear related to dissolution of the iron-rich FeS mineral, mackinawite, because IAP calculations on data from discrete bottle samples obtained from bottom waters are similar to the pKsp of mackinawite. Soluble iron-sulfide species are stable in the absence of O2 (both in lake waters and the pipeline) and transported several miles during power generation. However, iron-sulfide complexes can react with O2 to oxidize sulfide and can also dissociate releasing volatile H2S when the waters containing them are exposed to the atmosphere downstream of the powerplant. Sediment analyses show that the lake is rich in oxidized iron solids (both crystalline and amorphous). Fe concentrations in FeS solids are low (<5 μmole/grdry wt) and the pyrite concentration ranges from about equal to the solid FeS to 30 times the solid FeS concentration. The degree of pyritization is below 0.12 indicating that pyrite formation is limited by free sulfide, which can react with the iron-rich sulfide complexes.  相似文献   

20.
The coexistence of hydrogen-containing materials and radioactive substances in source rocks is universal. Few documents have researched whether the latter can radiate the former to generate hydrogen gas (H2) as well as the factors controlling this process. This work conducted a series of radiation experiments to address this issue. Samples were placed in sealed Pyrex glass containers and subject to cobalt (60Co) γ irradiation and components and contents of resultant gases were analyzed using gas-chromatography. The results show that all the samples released variable amounts of H2 after irradiation and that the yield (H2) of decane is lower than that of 3-tetradecylthiophene but higher than that of distilled water, which implies that a weaker H-X bond energy (X indicates O, C or other element) in homogeneous materials corresponds with increased yield (H2). The yields (H2) of samples decreased with the decreasing solutions concentrations in sequence from mixed salts solution, KCl solution, Yellow Sea water, oil field water, gypsum solution to distilled water. The experimental results also show that the yield (H2) of distilled water with montmorillonite is higher than that of distilled water with kaolinite, because due to the larger specific surface area, ion exchange capacity and more effective energy transfer effect of montmorillonite. Meanwhile, the irradiation of oxygen- and carbon-containing materials also releases O2 and CH4. The production of H2 via the irradiation of hydrogen-containing materials makes the involvement of exogenous H2 into hydrocarbon generation possible, which can enhance the hydrocarbon volume and optimize crude oil.  相似文献   

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