Dissociation constants of calcite and CaHC03+ from 0 to 50°C

From conductance measurements, the negative logarithm of the dissociation constant of the CaHCO₃₊ ion pair, pK(CaHCO₃⁺), is 0.7, 1.0 and 1.35 within ±0.05 units at 0, 25 and 60°C, respectively. A revaluation of published and unpublished data yields pK(CaCO₃⁰) ≈ 3.2 at 25°C. Use of these pK's to compute the dissociation constant of calcite (Kc) from published calcite solubility measurements in pure water gives pKc values which increase markedly with ionic strength. However, if the ion pairs are ignored, computed pKc values are nearly constant with ionic strength. All reasonable attempts to eliminate the trend in pKc by adjusting ion activity coefficients, and/or values of K(CaCO₃⁰) failed, so the dilemma remains. Kc values computed from the most reliable published calcite solubility data are in good agreement with such values based on solubility data measured in this study at 5, 15, 35 and 50°C. Study results ignoring ion pairs are accurately represented by the equation log Kc = 13.870 — (3059/T) ?0.04035T, and correspond to ?8.35, ?8.42, and ?8.635 at 0, 25 and 50°C, respectively. The logarithmic expression leads to ΔH_r^o = ?2420 ± 300 cal/mol, ΔCp = ?110 ± 2 cal/deg mol, and ΔS_r^o = ?46.6 ± 1.0 cal/deg mol for the calcite dissociation reaction at 25°C. The dependence of Kc on temperature when CaCO₃⁰ and CaHCO₃⁺ are assumed, is described by log Kc = 13.543 ? (3000/T) ? 0.0401T which yields ?8.39, ?8.47, and -8.70 at 0, 25 and 50°C. This gives ΔH_r^o = ?2585 ± 300 cal/mol, ΔCp = ?109 ± 2 cal/deg mol, and ΔS_r⁰ = ?47.4 ± 1.0 cal/deg mol at 25°C.     

An experimental study of crystalline basalt dissolution from 2 ? pH ? 11 and temperatures from 5 to 75 °C

Steady-state element release rates from crystalline basalt dissolution at far-from-equilibrium were measured at pH from 2 to 11 and temperatures from 5 to 75 °C in mixed-flow reactors. Steady-state Si and Ca release rates exhibit a U-shaped variation with pH where rates decrease with increasing pH at acid condition but increase with increasing pH at alkaline conditions. Silicon release rates from crystalline basalt are comparable to Si release rates from basaltic glass of the same chemical composition at low pH and temperatures ?25 °C but slower at alkaline pH and temperatures ?50 °C. In contrast, Mg and Fe release rates decrease continuously with increasing pH at all temperatures. This behaviour is interpreted to stem from the contrasting dissolution behaviours of the three major minerals comprising the basalt: plagioclase, pyroxene, and olivine. Calcium is primarily present in plagioclase, which exhibits a U-shaped dissolution rate dependence on pH. In contrast, Mg and Fe are contained in pyroxene and olivine, minerals whose dissolution rates decrease monotonically with pH. As a result, crystalline basalt preferentially releases Mg and Fe relative to Ca at acidic conditions. The injection of acidic CO₂-charged fluids into crystalline basaltic terrain may, therefore, favour the formation of Mg and Fe carbonates rather than calcite. Element release rates estimated from the sum of the volume fraction normalized dissolution rates of plagioclase, pyroxene, and olivine are within one order of magnitude of those measured in this study.     

Thermodynamics of hydration of Na- and K-clinoptilolite to 300 °C

The hydration state of Na- and K-exchanged clinoptilolite from Castle Creek (Idaho, U.S.A.) has been measured by a pressure titration method to 300 °C and P _H2O<30 bars. The water content of clinoptilolite can be predicted as a function of water activity and temperature with the equation: a _H2O = [exp[[−ΔH _h ^∘/nRT] + [ΔS _h ^∘/nR] − 1/nRT· [W₁ X _h + W₂ X _{h 2}]− ln(X _a/X _h)]]⁻¹ where T is degrees in Kelvin, ΔH _h ^∘ is the standard molal enthalpy of hydration, ΔS _h ^∘ is the entropy of hydration, X _h and X _a are, respectively, the mole fractions of the hydrous and anhydrous components of the solid solution, W ₁ and W ₂ are interaction parameters, n is the maximum number of moles of H₂O per formula unit (based on 12 oxygens), and R is the gas constant. This equation can be used to locate clinoptilolite-H₂O isohydrons in a _H2O-T space below the liquid-vapor equilibrium curve of water. The standard molal Gibbs free energy of hydration is −47.62 ± 5.52 kJ/mol H₂O and −5.40 ± 2.71 kJ/mol H₂O for the Na- and K-clinoptilolite, respectively. These standard-state thermodynamic properties of clinoptilolite hydration are in good agreement with previous data at low H₂O pressures. The experiments indicate that clinoptilolite progressively dehydrates with increasing temperature at pressures along the liquid-vapor equilibrium curve. Kinetic data above 150 °C show that clinoptilolite dehydration and hydration reactions are fast and reversible and that steady-state hydration states are attained in minutes. Received: 19 June 1998 / Revision, accepted 14 December 1998     

Partitioning and Hydrolysis of Nb and Ta and Their Implications with Regard to Mineralization

K₂NbOF₅ · H₂O and K₂TaF₇ were prepared through melting Nb₂O₅ and Ta₂O₅ respectively with KHF₂ · 2H₂O, followed by recrystallizing. The hydrolysis properties of K₂NbOF₅ and K₂TaF₇ were determined again by using a rapidly quench vessel. As temperature (from 250 to 550 °C) and pressure (from 500 to 1500 bars) increase, the degree of hydrolysis of both K₂NbOF₅ and K₂TaF₇ will increase. Nb- and Ta-fluorine complex compounds are instable in supercritical aqueous fluids. The degree of hydrolysis of both K₂NbOF₅ and K₂TaF₇ decreases with increasing concentration of HF, independent of the concentration of NaF. The partition coefficients of Nb and Ta between granitic melt and fluid phase are less than 0.15, i.e., most of Nb and Ta are left in granitic melt. The partition coefficient of Ta is more dependent on the concentration of HF than that of Nb. The significance of hydrolysis in Nb- and Ta- mineralization is also discussed in the present paper.     

Introduction to the Geological Map of Asia and Europe

ThenewlycompiledGeologicalMapofAsiaandEurope(1.5000000)wasoneoftheimportantmapsoftheMinistryofGeologyandMineralResources(MGMR)ofChinaforsubmittingtothe30thInternationalGeologicalCongress.ItwascompiledbytheinstituteofGeology,CAGS.ThemapincludesthewholeAsianandEuropeanterritories,covering50.71millionkm~2,withalengthof3.5mand2.5minwidth.Themainresearchresultsandgreatprogressshownonthemapareasbelow.1.Thegeographicalmap,basedonwhichthegeologicalmapwascompiled,hashighprecisioninmathematics…     

Characteristics of Karst Ecosystems of Vietnam and Their Vulnerability to Human Impact

Karst in Vietnam covers an area of about 60,000 km2, i.e. 18 % of the surface of the country. The country has an annual average temperature of 24@, an annual average rainfall of 2300 mm and a relative humidity of about 90%. Karst in Vietnam is typified by peak cluster-depression landscapes ranging in elevation from 200 to over 2000 m. Tower and coastal karst landscapes also exit. Because of naturally favourable conditions, karst ecosystems are diverse and very rich. Higher plants (cormophytes) are abundant. They are represented by approximately 2000 species, 908 genera, 224 families, 86 orders and 7 phyla. They form a thick vegetation cover of evergreen tropical rainforest. Knowledge about lower plants is limited. The fauna is rich and diverse. Phyla such as Protozoa, Vermes, Mollusca and Arthropoda are yet ill known. Preliminary results show that the phylum Chordata is represented by 541 species from 80 families, 40 orders and 5 classes. There exist many precious and rare mammals, in particular some en     

Remediation and restoration of metal-contaminated sites: Concepts and applications to mining areas

Metals, including heavy metals and metalloids, are a common group of environmental contaminants. Their sources in the environment are geogenic or anthropogenic. The growing trend in global industrialization ensures that more metals could be dispersed even…     

Application of the EnKF and Localization to Automatic History Matching of Facies Distribution and Production Data

The performance of the ensemble Kalman filter (EnKF) for continuous updating of facies location and boundaries in a reservoir model based on production and facies data for a 3D synthetic problem is presented. The occurrence of the different facies types is treated as a random process and the initial distribution was obtained by truncating a bi-Gaussian random field. Because facies data are highly non-Gaussian, re-parameterization was necessary in order to use the EnKF algorithm for data assimilation; two Gaussian random fields are updated in lieu of the static facies parameters. The problem of history matching applied to facies is difficult due to (1) constraints to facies observations at wells are occasionally violated when productions data are assimilated; (2) excessive reduction of variance seems to be a bigger problem with facies than with Gaussian random permeability and porosity fields; and (3) the relationship between facies variables and data is so highly non-linear that the final facies field does not always honor early production data well. Consequently three issues are investigated in this work. Is it possible to iteratively enforce facies constraints when updates due to production data have caused them to be violated? Can localization of adjustments be used for facies to prevent collapse of the variance during the data-assimilation period? Is a forecast from the final state better than a forecast from time zero using the final parameter fields?To investigate these issues, a 3D reservoir simulation model is coupled with the EnKF technique for data assimilation. One approach to enforcing the facies constraint is continuous iteration on all available data, which may lead to inconsistent model states, incorrect weighting of the production data and incorrect adjustment of the state vector. A sequential EnKF where the dynamic and static data are assimilated sequentially is presented and this approach seems to have solved the highlighted problems above. When the ensemble size is small compared to the number of independent data, the localized adjustment of the state vector is a very important technique that may be used to mitigate loss of rank in the ensemble. Implementing a distance-based localization of the facies adjustment appears to mitigate the problem of variance deficiency in the ensembles by ensuring that sufficient variability in the ensemble is maintained throughout the data assimilation period. Finally, when data are assimilated without localization, the prediction results appear to be independent of the starting point. When localization is applied, it is better to predict from the start using the final parameter field rather than continue from the final state.     

Remediation and restoration of metal-contaminated sites： Concepts and appfications to mining areas

Metals, including heavy metals and metalloids, are a common group of environmental contaminants. Their sources in the environment are geogenic or anthropogenic. The growing trend in global industrialization ensures that more metals could be dispersed even in pristine ecosystems. To fuel industrialization, more metal ore mines have to be discovered and explored. These explorations often result in landscape disturbance, soil degradation and environmental contamination by unwanted mining constituents. Mine tailings brought up to the ground surface often serve as the main source of contaminants when these pyrite-rich materials oxidize. The oxidation of mine tailings results in proton generation, coupled with the dissolution of metals and other cations Unwanted anionic constituents are also produced. The so-called ＂acid mine drainage＂ may affect the productivity of farmlands and stability of receiving streams and other bodies of water-acidifying the waters and enriching the ecosystem with metals, i.e., high total dissolved solids. The acidified overburden materials become inhospitable to plant and microbial life as they are typically low in organic matter content and infertile. This exposes the landscape to runoff and erosion.     

Hydrostatic compression and crystal structure of pyrope to 33 GPa

The equation of state and crystal structure of pyrope were determined by single crystal X-ray diffraction under hydrostatic conditions to 33 GPa, a pressure that corresponds to a depth of about 900 km in the lower mantle. The bulk modulus K _T0 and its pressure derivative K ^' _T0 were determined simultaneously from an unweighted fit of the volume data at different pressures to a third order Birch-Murnaghan equation of state. They are 171(2) GPa and 4.4(2), respectively. Over the whole pressure range, MgO₈ polyhedra showed the largest compression of 18.10(8)%, followed by AlO₆ and SiO₄ polyhedra, with compression of 11.7(1)% and 4.6(1)%, respectively. The polyhedral bulk moduli for MgO₈, AlO₆ and SiO₄ are 107(1), 211(11) and 580(24) GPa, respectively, with K ^' _T0 fixed to 4. Significant compression of up to 1.8(1)% in the very rigid Si−O bonding in pyrope could be detected to 33 GPa. Changes in the degree of polyhedral distortion for all three types of polyhedra could also be observed. These changes could be found for the first time for AlO₆ and SiO₄ in pyrope. It seems that the compression of pyrope crystal structure is governed by the kinking of the Al−O−Si angle between the octahedra and tetrahedra. No phase transition could be detected to 33 GPa. Received: 24 March 1997 / Revised, accepted: 29 July 1997     

Thermal transformations of akaganéite and lepidocrocite to hematite: assessment of possible precursors to Martian crystalline hematite

We examine the possibility that crystalline hematite (α-Fe₂O₃) deposits on Mars were derived from the precursor iron oxyhydroxide minerals akaganéite (β-FeOOH) or lepidocrocite (γ-FeOOH) and compare them to an earlier study of goethite (α-FeOOH) and magnetite (Fe₃O₄) precursors. Both the mid-infrared and visible/near infrared spectra of hematite are dependent upon the hematite precursor mineral and the temperature of transformation. Laboratory spectra are compared to spectra from the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) and the Mars Exploration Rover (MER) Opportunity Mini-TES and Pancam experiments, allowing us to infer the formation environment of Martian crystalline hematite deposits. Akaganéite and lepidocrocite readily transform to hematite at temperatures of 300 and 500°C, respectively. The visible/near-infrared and mid-infrared spectra of akaganéite-derived hematite are poor matches to data returned from TES, Mini-TES, and Pancam. The spectra of lepidocrocite-derived hematite are slightly better fits, but previously published spectra of goethite-derived hematite still represent the best match to MGS and MER spectral data. The experiments demonstrate that hematite precursor mineralogy, temperature of formation, and crystal shape exert a strong control on the hematite spectra.     

A thermodynamic model for the solubility of barite and celestite in electrolyte solutions and seawater to 200°C and to 1 kbar

This paper describes a model for barite and celestite solubilities in the Na–K–Ca–Mg–Ba–Sr–Cl–SO₄–H₂O system to 200°C and to 1 kbar. It is based on Pitzer's ion interaction model for the thermodynamic properties of the aqueous phase and on values of the solubility products of the solids revised in this work. It is shown how barite and celestite solubilities in electrolyte solutions can be accurately predicted as a function of temperature and pressure from previously determined Pitzer's parameters. The equilibrium constant for the BaSO₄(aq) ion pair dissociation reaction is calculated from recently reported barite solubility in Na₂SO₄ solutions from 0 to 80°C. Pressure corrections are evaluated through partial molal volume calculations and are partially validated by comparing model predictions to measured barite and celestite solubilities in pure water to 1 kbar and in NaCl solutions to 500 bars. The model is then used to investigate the tendency of ion pairing of Ca, Sr and Ba with sulfate in seawater. Finally, the activity coefficient of aqueous barium sulfate in seawater is calculated for temperature, pressure and salinity values found in the ocean and compared to published values.     

Can drying and re-wetting of magnesium sulfate salts lead to damage of stone?

Magnesium sulfate salts have been linked to the decay of stone in the field and in laboratory experiments, but the mechanism of damage is still poorly understood. Thermomechanical analysis shows that expansion of stone contaminated with magnesium sulfate salts occurs during drying, followed by relaxation of the stress during dehydration of the precipitated salts. We applied thermogravimetric analysis and X-ray diffractometry to identify the salt phases that precipitate during drying of bulk solutions. The results show the formation of 11 different crystal phases. A novel experiment in which a plate of salt-laden stone is bonded to a glass plate is used to demonstrate the existence of crystallization pressure: warping of the composite reveals significant deformation of the stone during re-wetting of lower hydrates of magnesium sulfate. Environmental scanning electronic microscope (ESEM)/STEM experiments show that hydration of single crystals of the lower hydrates of magnesium sulfate is a through-solution crystallization process that is only visible at a small scale (~μm). It is followed by growth of the crystal prior to deliquescence. This demonstrates that crystallization pressure is the main cause of the stress induced by salt hydration. In addition, we found that drying-induced crystallization is kinetically hindered at high concentration, which we attribute to the low nucleation rate in a highly viscous magnesium sulfate solution.     

Behaviour of Elements during Granite Formation and Its Relationship to Mineral-Zonation

Please refer to the attachment(s) for more details.     

Evolution of Chinese Neogene Rhinocerotidae and Its Response to Climatic Variations

Chinese Neogene Rhinocerotidae has quite a complete record and its temporal range is the Early Miocene to Late Pliocene. The samples include 25 species in 4 tribes of 2 subfamilies. They are used as a foundation for the study of the evolution of the family and its relation to climatic changes. Taxonomic diversity, new records and extinctions are estimated for each Chinese Neogene mammal faunal unit (NMU). The diversity of Chinese Rhinocerotidae varies noticeably throughout the Neogene and is recognized within five stages: the Middle Miocene and Late Miocene are stages of high diversity and the Early Miocene, early Late Miocene and Pliocene are stages of low diversity. Rhinocerotid diversity and morphology are closely related to environmental factors and particularly sensitive to changes in ambient temperature and humidity. The interpretation of climatic variation reflected in the evolution of Rhinocerotidae corresponds precisely with the conclusions drawn from other workers and provides new evidence fen     

Refinement of the structure of ζ-Nb2O5 and its relationship to the rutile and thoreaulite structures

Summary The crystal structure of -Nb₂O₅, space groupC2/c, a 12.740(2),b 4.8830(6),c 5.5609(6)Å, 105.02(1)°, Z 4, has been refined toR 1.6% for 457 observed reflections (MoK). The coordination polyhedron of the niobium atom is a distorted octahedron; the crystal structure consists of two-octahedron-thick, rutile-like layers separated by crystallographic shear (CS) planes. Relative to the rutile structure, these planes are indexed (101) and adjacent layers are related by the CS vector <a/6b/2c/2>. Members of the thoreaulite-foordite series have topologically identical two-octahedron-thick (101) sheets; however, here the CS vector Zusammenfassung Die Kristallstruktur des -Nb₂O₅, Raumgruppe C2/c, a 12,740(2),b 4,8830(6),c 5,5609(6) Å, 105,02(1)°,Z 4, wurde mit 457 beobachteten Reflexen (MoK) aufR 1,6% verfeinert. Das Koordinationspolyeder des Niobiumatoms ist ein verzerrtes Oktaeder; die Kristallstruktur besteht aus Rutil-artigen Schichten, die zwei Oktaeder dick sind und von kristallographischen Scher-(CS-)flächen getrennt werden. In bezug auf die Rutilstruktur haben diese Flächen die Indizes (101) und benachbarte Schichten sind durch den CS-Vektor <a/6b/2c/2> verknüpft. Die Glieder der Thoreaulith-Foordit-Reihe haben idente (101)-Schichten einer Dicke von zwei Oktaedern; indessen bewirkt hier der CS-Vektor <a/2> _r gekoppelt mit dem Translationsvektor <1,5c> _r die Einlagerung von tetragonal-antiprismatischen Lücken zwischen benachbarte Schichten.

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With 4 Figures     

The major ion, δCa, δCa, and δMg geochemistry of granite weathering at pH = 1 and T = 25 °C: power-law processes and the relative reactivity of minerals

We dissolved Boulder Creek Granodiorite in a plug flow reactor for 5794 h at pH = 1 and T = 25 °C. The primary purpose of the experiment was to identify controls on dissolved δ^44/40Ca, δ^44/42Ca, and δ^26/24Mg values during granite weathering. Herein, we also examine the origin of Ca and Mg isotopic variability among minerals composing the Boulder Creek Granodiorite, and we constrain fundamental characteristics of granite weathering important for quantifying the elemental and isotopic geochemistry of the reactor output. Nine Ca-bearing minerals display an 8.80‰ range of δ^44/40Ca values and a 0.51‰ range of δ^44/42Ca values. Three Mg-bearing minerals display a 1.53‰ range of δ^26/24Mg values. These ranges expressed at the mineralogical scale are higher than the ranges thus far reported for bulk igneous rocks. Most of the δ^44/40Ca variability reflects ⁴⁰Ca enrichment in K-feldspar, and to a lesser extent, biotite, due to the radioactive decay of ⁴⁰K over the 1.7 Ga age of the rock, whereas the entire range of δ^44/42Ca values reflects mass-dependent isotope fractionation during igneous differentiation and crystallization. The range of δ^26/24Mg values may represent either fractionation during the chloritization of biotite or interaction of the Boulder Creek Granodiorite with Mg-rich metamorphic fluids having low δ^26/24Mg values.The elemental and isotopic composition of the reactor output varied substantially during the experiment. We synthesize the mineralogical and fluid data using coupled mass-conservation equations solved at non-steady-state. Model calculations reveal an intricate balance between increasing specific surface area and decreasing mineral concentrations. While surface area normalized dissolution rate constants were time-invariant, specific surface area increased as a power-law function of time through positive feedbacks between mechanical disaggregation, chemical dissolution, and mineral depletion. Variations in dissolved δ^44/40Ca, δ^44/42Ca, and δ^26/24Mg values reflect conservative mixing rather than fractionation. Apatite and calcite initially control δ^44/40Ca and δ^44/42Ca values, followed by biotite, titanite, epidote, hornblende, and plagioclase. The release of radiogenic ⁴⁰Ca clearly defines the period where biotite dissolution dominates. The brucite layer of chlorite initially controls δ^26/24Mg values, followed by biotite, the TOT layer of chlorite, and hornblende. Through direct isotopic tracking, these results demonstrate that trace minerals, such as apatite and calcite in the case of Ca and brucite in the case of Mg, dominate elemental release during the incipient stages of granite weathering. The results further show that biotite dissolution dominates the middle stages of granite weathering and that plagioclase dissolution only becomes important during relatively late stages. The Ca and Mg isotope variations associated with these stages are distinct and potentially resolvable in soil mineral weathering studies.     

From matters of fact to places of concern? Energy,environmental movements and place-making in Chile and Thailand

As demand for energy is growing and resources become scarcer, energy increasingly becomes the site of heated controversies. In Latour’s terms, energy turns from a “matter of fact” into a “matter of concern”. In these energy controversies, environmental movements frequently play a central role, highlighting what is at stake in these developments. While these movements have often been studied, these studies rarely focus on the interaction between controversies, environmental movements, and place-making. In this article, we not only argue that energy is frequently turned from matter of fact into a matter of concern, but that this argument also extends to the notion of place. As such, energy controversies turn villages, cities, or regions themselves into “places of concern”. The article delves deeper into the production of places of concern through two case studies of energy controversies around power plants: a proposed coal plant in Bo Nok, Thailand, and HidroAysen, a hydropower project in Chilean Patagonia. We specifically focus on the issues that were opened up for debate in both countries, and on the role of environmental movements in the production of these places. Our examples are based on fieldwork and interviews in these two areas, as well as media and document analysis. While the two cases are from two different countries, we nonetheless find surprising parallels between them. These insights are instrumental to link theoretical debates on controversies and place-making. Moreover, they provide empirical insights into the transformative and lasting effects of energy controversies on people and places.     

Searching for the boundaries and correlation of the Jurassic： from base to top and from shelf to basin The Fourth International Symposium of IGCP 506

Following the successful 1st IGCP 506 sym- posium in Nanjing （Nov. 2005）, the 2nd Workshop in Beijing, China （during the IPC2006, June 2006） and the 3rd Workshop in Krakow of Poland （Sept. 2006）, the Inter- national Geoscience Programme IGCP 506 organized its fourth international symposium from 4-8 July, 2007 in the University of Bristol, UK. The symposium focused on the topics of biodiversity of fauna, flora, palaeoenvi- ronment and stratigraphy,     

Introduction to concepts and proposed standardization of the term “Quaternary”

During the early 1800‘s, the current Cenozoic Era (Phillips,1840) underwent competing schemes of subdivision based on field relationships or on biological evolution.