全球温度变化的热力学平衡和最新发现

本文提出了一种新的研究全球气候温度变化的思路。为发现全球气候变化的宏观规律,把生物圈系统作为一个整体的物质进行研究,从而把纷繁复杂的全球气候温度变化问题归纳成经典物理学的热量与温度变化问题。给出了广义生物圈的热平衡测量Q值和温度变化的热力学公式,并在实际数据的基础上通过计算发现人类使用矿物燃料和核能所排放的热量理论上可使全球海平面每年升高35 mm或者可使大气对流层温度每年升高011 ℃。该发现表明:能源热量因素已成为影响全球温度变化的重要因素。     

The types and mechanisms of metasomatism

Metasomatism is considered as a group of various replacement phenomena - the effect of pore fluids and surface energy at the solid-fluid interface. Various types of metasomatism are identified, dependent on the volume of equilibrium mineral-forming systems and types of equilibrium, distance of mass-exchange, stage nature of the metasomatic process, energy of the active fluid, relationship between metasomatism and other types of replacement, and its molecular mechanism. The physicochemical types and elements of molecular physics and the kinetics of metasomatism are discussed. -- Author.     

Fe2+-Mg order-disorder in orthopyroxene: equilibrium fractionation between the octahedral sites and thermodynamic analysis

The equilibrium intracrystalline distribution coefficient, k _D ^*, of Fe^* (i.e. Fe²⁺ + Mn) and Mg between the M1 and M2 sites of three natural nearly binary Fe²⁺-Mg orthopyroxene crystals (Fs₁₄, Fs₁₅ and Fs₄₉) were determined by annealing experiments at several temperatures between 550 and 1000 °C and single crystal X-ray structure refinements. In addition, the X-ray data of an orthopyroxene crystal (Fs₂₃), which were collected earlier by Molin et al. (1991) between 700 and 1000 °C, were re-refined. The data were processed through two different refinement programs (SHELXL-93 and RFINE90) using both unit and individual weights and also both ionic and atomic scattering factors. The calculated site occupancies were found to agree within their estimated standard errors. However, the use of ionic scattering factors led to significantly better goodness of fit and agreement index, and smaller standard deviations of the site occupancies than those obtained from the use of atomic scattering factors. Furthermore, the weighted refinements yielded significantly smaller standard deviations of the site occupancies than the unweighted refinements even when the same set of reflections was used in the two procedures. The site occupancy data from this study were combined with selected published data to develop expressions of k _D ^* as a function of temperature and composition. Calculation of the excess configurational entropy, ΔS ^XS, suggests that orthopyroxene should be treated as a two parameter symmetric solution instead of as a “simple mixture”. The calculated ΔS ^XS values and the excess Gibbs free energy of mixing suggested by available cation exchange data lead to a slightly negative enthalpy of mixing in the orthopyroxene solid solution. Received: 25 August 1998 / Accepted: 10 March 1999     

Carbon dioxide in igneous petrogenesis: II. Fluid dynamics of mantle metasomatism

Petrographic, fluid inclusion, geochemical and isotopic evidence from xenoliths in alkali basalts suggests that low-viscosity fluids rich in O-H-C, dissolved silicates and especially the incompatible elements may ascend, decompress and precipitate crystalline phases and/or induce partial fusion in the upper mantle. Such mantle metasomatic fluids (MMF) may be important in generating isotopic heterogeneity and in transporting and focusing mantle heat. In order to model the movement of MMF, the ordinary differential equations governing the variation ofP, T, ascent velocity and fluid density of a compressible, viscous, single-phase (H₂O or CO₂) non-reacting fluid ascending through a vertical crack of constant width have been solved. A large number of numerical simulations were carried out in which the significant factors affecting flow behavior (thermodynamic and transport fluid properties, roughness and width of cracks, geothermal gradient, initial conditions, etc.) were systematically varied. The calculations show that: (1) MMF tends to move at uniform rates following a short period of rapid initial acceleration, (2) MMF ascends nearly isothermally, (3) MMF acts as an efficient heat transfer agent; numerical experiments show that transport of heat into regions undergoing metasomatism can lead to partial fusion. The heat transported by movement of MMF averaged over the age of the Earth is sufficient to generate about 0.1 km³ of basaltic magma per year, which is approximately equal to the production rate of alkaline magma. If an intense period of mantle degassing occured early in the history of the Earth, the transport of heat and mass (K, U, Rb, LREE) by migrating fluids might have been important.     

Scales of equilibrium and disequilibrium during cleavage formation in chlorite and biotite-grade phyllites, SE Vermont

Detailed electron microprobe analyses of phyllosilicates in crenulated phyllites from south‐eastern Vermont show that grain‐scale zoning is common, and sympathetic zoning in adjacent minerals is nearly universal. We interpret this to reflect a pressure‐solution mechanism for cleavage development, where precipitation from a very small fluid reservoir fractionated that fluid. Multiple analyses along single muscovite, biotite and chlorite grains (30–200 μm in length) show zoning patterns indicating Tschermakitic substitutions in muscovite and both Tschermakitic and di/trioctahedral substitutions in biotite and chlorite. Using cross‐cutting relationships and mineral chemistry it is shown that these patterns persist in cleavages produced at metamorphic conditions of chlorite‐grade, chlorite‐grade overprinted by biotite‐grade and biotite‐grade. Zoning patterns are comparable in all three settings, requiring a similar cleavage‐forming mechanism independent of metamorphic grade. Moreover, the use of ⁴⁰Ar/³⁹Ar geochronology demonstrates this is true regardless of age. Furthermore, samples with chlorite‐grade cleavages overprinted by biotite porphyroblasts suggest the closure temperatures for the diffusion of Al, Si, Mg and Fe ions are greater than the temperature of the biotite isograd (>～400 °C). Parallel and smoothly fanning tie lines produced by coexisting muscovite–chlorite, and muscovite–biotite pairs on compositional diagrams demonstrate effectively instantaneous chemical equilibrium and probably indicate simultaneous crystallization. These results do not support theories suggesting cleavages form in fluid‐dominated systems. If crenulation cleavages formed in systems in which the chemical potentials of all major components are fixed by an external reservoir, then the compositions of individual grains defining these cleavages would be uniform. On the contrary, the fine‐scale chemical zoning observed probably reflects a grain‐scale process consistent with a pressure‐solution mechanism in which the aqueous activities of major components are defined by local dissolution and precipitation. Thus the role of fluids was probably limited to one of catalysing pressure‐solution and fluids apparently did not drive cleavage development.     

Estimation of crystallization proportions and the equilibrium/disequilibrium of quench experiments in the basite systems

Original program based on Huang algorithm was used to calculate the concentrations of coexisting phases in quench experiments with the known bulk compositions of systems and phases. Using this procedure, we rejected the disequilibrium experiments from experimental series with the similar bulk (starting) composition of charge and calculated crystallization proportions for the olivine-plagioclase and olivine-plagioclase-augite cotectics. The statistically valid dependence was established for the first time between crystallization proportions for the olivine-plagioclase cotectics and #An of the melt. Experimentally obtained data on the Ol-Pl and Ol-Pl-Aug crystallization proportions were compared with values obtained by numerical simulation of the equilibrium crystallization of basaltic melts using COMAGMAT software. It was shown that the basic version COMAGMAT-3.5 Program with a standard set of liquidus thermometers satisfactorily reproduces the crystallization proportions in these cotectics for basaltic melts. Simulation of crystallization for more silicic magmas requires calibrating liquidus thermometers for modeled compositional range. Only single experimental estimates were obtained for other cotectics.     

The stability of laihunite—A thermodynamic analysis

Laihunite, a mineral of ferric and ferrous iron silicate discovered in China in recent years, occurs in high grade metamorphic BIF coexisting with magnetite, quartz, fayalite, ferrosilite and almandinc. Complete nets based on Schreinemakers bundles and partial nets with maximum closure after the method described by H. W. Day have been constructed by taking into account the existence of this mineral in order to illustrate phase relations for the (n+3) multisystem in the system Fe₂O₃-FeO-SiO₂. Judging from Lindsley’s experimental data on ferrosilite, laihunite-ferrosilite assemblage is expected to be stable at pressures probably higher than 15 kb. Two-pyroxene and garnet-clinopyroxene geothermometers gave the temperatures of formation between 600–700°C. The free energy of laihunite calculated according to Chen’s method and estimated heat capacity power-function coeficients allow oxygen fugacity to be plotted against temperature at different total pressure swith respect to a number of univariant reactions in which laihunite is involved. The logfo ₂-T diagram demonstrates that to a first approximation the stability field of laihunite overlaps the upper part of the magnetite field, but its upper limit is a little beyond the hematite-magnetite equilibrium. The three major requirements for laihunite stability, i.e., an unusual high pressure, a temperature in the order of 600°C–700°C and a relatively higher oxygen fugacity, are mutually exclusive in common geological environment, which may probably account for the rare occurrence of this mineral in nature. For the BIF in which laihunite occurs, the pressure caused by the weight of overlying strata is not high enough to give rise to its formation even in the extreme case of geothermal gradient. So it is suggested that additional tectonic pressure in response to plate activity might have been involved.     

Sulphur isotopic fractionation between sulphate and sulphide in hydrothermal ore deposits: disequilibrium vs equilibrium processes

Correlative fractionation relationships of sulphur isotope data for coexisting sulphate and sulphide pairs from hydrothermal ore deposits on δ³⁸S versus Δ³⁴S diagrams are deciphered theoretically. Taking into account dissolved H₂S and SO₄^2- in hydrothermal fluids during precipitation of both sulphate and sulphide minerals, a 4-species closed system is suggested for describing the conservation of mass among all sulphur-bearing species on the δ-Δ diagrams. The covariation in the δ³⁴S values of both sulphate and sulphide is ascribed to isotopic exchange between oxidized and reduced sulphur species during mineral precipitation. The isotopic exchange could be a thermodynamic process due to simple cooling of high temperature fluids, which results in an equilibrium fractionation, or a kinetic process due to mixing of two sulphur reservoirs, which leads to a disequilibrium fractionation. The δ³⁴S value of total sulphur in a hydrothermal system could change due to the precipitation of minerals, or due to the escape of H₂S and/or SO₄^2-. Sulphur isotope data for anhydrite and pyrite pairs from the Luohe porphyrite iron deposit in the Yangtze River Valley is used to illustrate the mixing responsible for the disequilibrium fractionation.     

Kinetic,equilibrium and thermodynamic studies of thiamethoxam adsorption by multi-walled carbon nanotubes

Because of their high adsorption capacity, carbon nanotubes have caught the attention of the scientific community and a number of experimental results confirmed their ability to adsorb many toxins from water. The aim of this work was to study the kinetics, equilibrium and thermodynamics of thiamethoxam adsorption by multi-walled carbon nanotubes in aqueous solutions. To further elucidate the influence of nanotube structure on the adsorption mechanism, the experiments were performed on both fresh (pristine) and nitric acid-modified multi-walled carbon nanotubes. The results of the kinetic studies were analyzed using three kinetic models, while the adsorption equilibrium was tested against four different adsorption models. Based on the results, and the physico-chemical properties of the adsorbent and adsorbate, it is proposed that the dominant mechanism for thiamethoxam molecules attaching to multi-walled carbon nanotubes is caused by aromatic π–π interactions (electron donor–acceptor interactions). The results of thermodynamic calculations based on the adsorption data indicate the exothermic nature of the process, regardless of the carbon nanotube type used. The decrease in entropy and the consequent negative change in Gibbs free energy, as expected, confirm the spontaneity of thiamethoxam adsorption on both pristine and functionalized multi-walled carbon nanotubes.     

Distribution of elements in coexisting minerals and the problem of chemical disequilibrium in metamorphosed basic rocks

Distribution of elements in coexisting minerals—biotite, hornblende, augite, hypersthene and plagioclase in charnockitic rocks of West Uusimaa Complex, Finland, is mostly orderly indicating a close approach to chemical equilibrium. The distribution of iron and magnesium in coexisting hornblende and pyroxenes of basic charnockites and other rocks of granulite facies from several different areas is also orderly but the variation in the fugacities of H₂O and H₂ may cause a disorderly distribution locally in some rocks. The probable oxidation or reduction reactions are discussed on the basis of thermochemical and mineralchemical data.     

High U/Th partitioning by clinopyroxene from alkali silicate and carbonatite metasomatism: an origin for Th/U disequilibrium in mantle melts?

Clinopyroxene/melt pairs in strongly potassic silicate and carbonatite melts exhibit unusually high U/Th partitioning ratios of ˜ 3 and ˜ 2, respectively. These values are much higher than those found for aluminous clinopyroxenes in peridotite, and have the potential to cause significant (²³⁰Th)/(²³⁸U) isotope enrichment in volcanics. The potassic silicate (lamproite) and carbonatite melts correspond closely to the main agents of mantle metasomatism, indicating that clinopyroxene in metasomatized regions of the mantle may greatly affect U/Th disequilibria. Recycling of alkali pyroxenite veins in the oceanic lithosphere formed by solidification of melt in the extremities of the MORB melting region presents an alternative to eclogite recycling in MORB and OIB genesis.     

Natural gas at thermodynamic equilibrium Implications for the origin of natural gas

It is broadly accepted that so-called 'thermal' gas is the product of thermal cracking, 'primary' thermal gas from kerogen cracking, and 'secondary' thermal gas from oil cracking. Since thermal cracking of hydrocarbons does not generate products at equilibrium and thermal stress should not bring them to equilibrium over geologic time, we would not expect methane, ethane, and propane to be at equilibrium in subsurface deposits. Here we report compelling evidence of natural gas at thermodynamic equilibrium. Molecular compositions are constrained to equilibrium,

Possible relation of resistance of rocks to granitization and to their equilibrium and thermodynamic anisotropism

Resistance or susceptibility of different rocks to granitization and ultra metamorphism may be related to the degree of their equilibrium and to their energetic (thermodynamic) anisotropism. All rocks may be divided accordingly into active and passive ones, depending on their behavior in granitizing environments. The active group (sedimentary, elastic, clayey, mixed, noncrystalline effusives) consists of energetically anisotropic ones as well as of rocks that failed to attain their chemical equilibrium by the time of their stabilization. Such rocks are able to release a part of their energy in a certain stage of their granitization. The passive group includes sedimentary rocks (carbonate, ferruginous), fully crystalline magmatic rocks, energetically isotropic homogeneous sandstones, and quartzites). Granitization of such rocks, is, among other things, an endothermal phenomenon. Basic and ultrabasic magmatic rocks are susceptible to granitization, provided they are interbedded with water-bearing sediments (including the passive ones); the resistance of such combinations to granitization is lower than the resistance of their constituents separately. Exothermal phenomena in granitization, such as release of energy from thermodynamically anisotropic bodies or of the accumulated solar energy (by crystalline substance) in reactions involving an uptake of liquid and gaseous phases, insufficient as they may be to assure a continuity of the granitization, may have a decisive effect upon the granitization-resistance of the rocks. — V.P. Sokoloff     

千将坪滑坡三维极限平衡分析

千将坪滑坡位于长江南岸支流青干河左岸,是三峡水库蓄水一个月后发生的水库新生型滑坡。通过千将坪滑坡恢复到原貌,采用三维极限平衡法对滑坡的整体稳定性和失稳下滑的触发因素进行了分析,探讨了水库蓄水和连续降雨对滑坡稳定性的影响。计算分析成果表明,水库蓄水后的浸泡软化作用使滑坡体稳定条件急剧恶化,蓄水和强降雨的联合作用最终导致千将坪滑坡产生大规模深层滑动。     

The role of speciation in alkaline igneous fluids during fenite metasomatism

Fenites associated with alkaline igneous rocks show a progression from a high temperature assemblage consisting of sodium-rich alkali feldspar + a sodium-ironrich mafic mineral, to an extreme end member assemblage consisting of pure potassium feldspar + iron oxide. The latter assemblage is only found in association with low temperature carbonatites. Segments of this distribution trend can be found in the contact aureole of single intrusive centers.In the east African Kisingiri nephelinite volcano, ijolite intruded a granodioritic basement, producing a fenitized contact aureole. During metasomatism of granodiorite, according to the mass balance model of Rubie (1982), feldspar only participated in an alkali exchange reaction, while quartz was replaced by sodic pyroxene. Outward from the intrusive contact, with decreasing temperature, feldspar became progressively K-enriched, while pyroxene was enriched in the acmite component. It is predicted that alkaliexchange reactions were controlled by NaCl⁰-KCl⁰ aqueous complexes close to the intrusive contact, while further out in the aureole Na⁺-K⁺ ions dominated at the lower temperatures and enhanced the level of potassium metasomatism of feldspar. With decreasing temperature in the aureole, the K/Na ratio of the fluid decreased and consequently the activity of acmite increased.Around carbonatites, where the level of CO₂ in the escaping fluid can be expected to be high, Na₂CO ₃ ⁰ -K₂CO ₃ ⁰ complexes may dominate. Alkali exchange between feldspar and these aqueous species enhances, even further, the stabilization of pure potassium feldspar. Boiling may also play an important role in potassium metasomatism as carbonatites are frequently associated with pyroclastic rocks. Formation of hematite instead of sodic pyroxene may be attributed to low , high and a CO₂-rich fluid.Important variables which determine the products of alkali metasomatism are shown to be temperature, pressure and CO₂ content of the fluid, as well as the K/Na ratio of the fluid.     

天津市浅层地热能存在的热堆积问题及解决方法探讨

通过对天津市浅层地热能地质环境动态监测系统获得的地埋管换热器周围温度场动态变化数据的归纳分析,得出以下结论:大部分地源热泵工程能满足建筑供暖制冷需求,地埋管换热器周围土壤在运行一个制冷供暖周期后能恢复到原始地温,不会对地质环境产生影响;一小部分地源热泵不能满足建筑制冷供暖需求,地埋管出水温度不能达到设计要求,换热器周围土壤温度出现持续的升高,在下一个制冷供暖周期不能恢复到原始地温,存在热堆积问题.在分析存在问题的基础上,提出以下可行解决方法:增加换热孔间距、调整换热孔群布置方式、地埋管与抽水井耦合开发利用、复合式供暖制冷系统以及深浅间隔布置的换热孔设计方式.     

An analysis of uncertainty in non-equilibrium and equilibrium geothermobarometry

In statistically optimised P–T estimation, the contributions to overall uncertainty from different sources are represented by ellipses. One source, for a diffusion‐controlled reaction at non‐equilibrium, is diffusion modelling of the reaction texture. This modelling is used to estimate ratios, Q, between free‐energy differences, ΔG, of reactions among mineral end‐members, to replace the equilibrium condition ΔG = 0. The associated uncertainty is compared with those already inherent in the equilibrium case (from end‐member data, activity models and mineral compositions). A compact matrix formulation is introduced for activity coefficients, and their partial derivatives governing error propagation. The non‐equilibrium example studied is a corona reaction with the assemblage Grt–Opx–Cpx–Pl–Qtz. Two garnet compositions are used, from opposite sides of the corona. In one of them, affected by post‐reaction Fe, Mg exchange with pyroxene, the problem of reconstructing the original composition is overcome by direct use of ratios between chemical‐potential differences, given by the diffusion modelling. The number of geothermobarometers in the optimisation is limited by near‐degeneracies. Their weightings are affected by strong correlations among Q ratios. Uncertainty from diffusion modelling is not large in comparison with other sources. Overall precision is limited mainly by uncertainties in activity models. Hypothetical equilibrium P–T are also estimated for both garnet compositions. By this approach, departure from equilibrium can be measured, with statistical uncertainties. For the example, the result for difference from equilibrium pressure is 1.2 ± 0.7 kbar.     

The Finero phlogopite-peridotite massif: an example of subduction-related metasomatism

The Finero peridotite massif is a harzburgite that suffered a dramatic metasomatic enrichment resulting in the pervasive presence of amphibole and phlogopite and in the sporadic occurrence of apatite and carbonate (dolomite)-bearing domains. Pyroxenite (websterite) dykes also contain phlogopite and amphibole, but are rare. Peridotite bulk-rock composition retained highly depleted major element characteristics, but was enriched in K, Rb, Ba, Sr, LREE (light rare earth elements) (La_N/Yb_N = 8–17) and depleted in Nb. It has high radiogenic Sr (⁸⁷Sr/⁸⁶Sr₍₂₇₀₎ = 0.7055–0.7093), low radiogenic Nd (ɛNd₍₂₇₀₎= −1 to −3) and EMII-like Pb isotopes. Two pyroxenite – peridotite sections examined in detail show the virtual absence of major and trace element gradients in the mineral phases. In both rock types, pyroxenes and olivines have the most unfertile major element composition observed in Ivrea peridotites, spinels are the richest in Cr, and amphibole is pargasite. Clinopyroxenes exhibit LREE-enriched patterns (La_N/Yb_N ∼16), negative Ti and Zr and generally positive Sr anomaly. Amphibole has similar characteristics, except a weak negative Sr anomaly, but incompatible element concentration ∼1.9 (Sr) to ∼7.9 (Ti) times higher than that of coexisting clinopyroxene. Marked geochemical gradients occur toward apatite and carbonate-bearing domains which are randomly distributed in both the sections examined. In these regions, pyroxenes and amphibole (edenite) are lower in mg## and higher in Na₂O, and spinels and phlogopite are richer in Cr₂O₃. Both the mineral assemblage and the incompatible trace element characteristics of the mineral phases recall the typical signatures of “carbonatite” metasomatism (HFSE depletion, Sr, LILE and LREE enrichment). Clinopyroxene has higher REE and Sr concentrations than amphibole (^amph/cpxD_REE,Sr = 0.7–0.9) and lower Ti and Zr concentrations. It is proposed that the petrographic and geochemical features observed at Finero are consistent with a subduction environment. The lack of chemical gradients between pyroxenite and peridotite is explained by a model where melts derived from an eclogite-facies slab infiltrate the overhanging harzburgitic mantle wedge and, because of the special thermal structure of subduction zones, become heated to the temperature of the peridotite. If the resulting temperature is above that of the incipient melting of the hydrous peridotite system, the slab-derived melt equilibrates with the harzburgite and a crystal mush consisting of harzburgite and a silica saturated, hydrous melt is formed. During cooling, the crystal mush crystallizes producing the observed sequence of mineral phases and their observed chemical characteristics. In this context pyroxenites are regions of higher concentration of the melt in equilibrium with the harzburgite and not passage-ways through which exotic melts percolated. Only negligible chemical gradients can appear as an effect of the crystallization process, which also accounts for the high amphibole/clinopyroxene incompatible trace element ratios. The major element refractory composition is explained by an initially high peridotite/melt ratio. The apatite, carbonate-bearing domains are the result of the presence of some CO₂ in the slab-derived melt. The CO₂/H₂O ratio in the peridotite mush increased by crystallization of hydrous phases (amphibole and phlogopite) locally resulting in the unmixing of a late carbonate fluid. The proposed scenario is consistent with subduction of probably Variscan age and with the occurrence of modal metasomatism before peridotite incorporation in the crust. Received: 20 July 1998 / Accepted: 28 October 1998     

The economics of the marine sector: general equilibrium and ecological analysis

Recent transfers of potential marine wealth to coastal states, resulting from the Third United Nations Convention on the Law of the Sea, have enhanced our awareness that the marine sector might ultimately prove to be a new frontier. The objective of this paper is to initiate work toward the development of a systematic appraoch to the economics of this sector. To this end, the marine sector is assumed to be the fourth factor of production, taking its place with the traditional trio of land, capital and labor. The productivity of this sector is described and analyzed with the aid of a simple general equilibrium model.     

Soil nailed slope by strength reduction and limit equilibrium methods

A detailed study of nailed slopes under different conditions is reported in this paper. No major difference is found in terms of safety and slip surfaces between the strength reduction method (SRM) and the limit equilibrium method (LEM) in general cases. Appreciable differences between the SRM and LEM appear, however, if the nail load is controlled by the overburden stress. Some special slip surfaces from the SRM obtained by using a very fine mesh are discussed. Field tests demonstrated that the nail head is important in determining the failure mode and the factor of safety of a nailed slope, while the effect of the nail elastic modulus is more noticeable only when the slope is very steep. The optimum layout of the soil nail was found to be longer at bottom and shorter at the top, which is contrary to some engineers’ guidelines for soil nail design during top-down construction. The distribution of tensional force along the soil nail is influenced by the state of the slope (service state, limit state) and the failure modes (external failure, internal failure). In general, the line of maximum tension may not correspond to the critical slip surface as commonly believed, except for the case where the failure mode is an internal tensile failure.