Experimental and theoretical study of the vibrational properties of diaspore (α-AlOOH)

Vibrational properties of diaspore, α-AlOOH, have been re-investigated using room-temperature single-crystal Raman spectroscopy and low-temperature powder infrared (IR) transmission spectroscopy. First-principles harmonic calculations based on density functional theory provide a convincing assignment of the major Raman peaks and infrared absorption bands. The large width of the Raman band related to OH stretching modes is ascribed to mode–mode anharmonic coupling due to medium-strength H-bonding. Additional broadening in the powder IR spectrum arises from depolarization effects in powder particles. The temperature dependence of the IR spectrum provides a further insight into the anharmonic properties of diaspore. Based on their frequency and temperature behavior, narrow absorption features at ~2,000 cm⁻¹ and anti-resonance at ~2,966 cm⁻¹ in the IR spectrum are interpreted as overtones of fundamental bending bands.     

Effect of γ-irradiation on clays and organoclays: a Mössbauer and XRD study

The interaction of γ-rays with smectite clays induces noticeable changes in the structure and physicochemical properties of the minerals. For sodium-montmorillonite, Mössbauer spectra show that γ-irradiation causes a partial reduction of trivalent iron to the divalent state due to hydrogen radicals production from the radiolysis of interlayer water. The XRD results show no change in the interlayer space upon irradiation and therefore the radiolysis of interlayer water causes no measurable changes in the architectural organization of the interlayer environment. Intercalation of simple organic molecules (ethylene glycol, tert-butanol and tetraalkylammonium salts) causes partial oxidation of structural divalent iron and affects the Mössbauer parameters of the M₁ and M₂ ferric components. Irradiation of ethylene glycol- or tert-butanol-clay composites indicates reduction of trivalent iron to the divalent state. XRD data show that the irradiation of clay-ethylene glycol complex causes collapse of the initial double layer of glycol molecules to a single layer complex. Finally, XRD results show that the effects of γ-irradiation on clay-tetraalkylammonium complexes depend upon the chain length of the organic cations.     

The effect of γ-irradiation on the structure and subsequent thermal decomposition of brucite

The effect of γ-irradiation on the structure, phase composition and kinetics of isothermal decomposition of natural textural brucite Mg(OH)₂ has been investigated by Mn²⁺ electron paramagnetic resonance (EPR), proton magnetic resonance (PMR), X-ray diffraction (XRD) and weight loss methods. Starting from a 10⁶-Gy dose, γ-irradiation (⁶⁰Co, 13.8 Gys^?1) is found to stimulate the formation of a new phase in the brucite structure, namely basic magnesium carbonate. The carbonate phase is assumed to form in brucite under γ-irradiation accordingly to the scheme \(\) (in the brucite structure). There is also a possibility that γ-irradiation forms particles with high reaction ability, CO^?₂ radicals and/or CO molecules, which can react with the brucite structure. Preliminary γ-irradiation (9.75 × 10⁷ Gy) slows down the subsequent isothermal dehydroxylation of natural brucite, which can be explained by the formation of the new carbonate phase in the Mg(OH)₂ structure. Dehydroxylation kinetics of both original and irradiated samples are interpreted by a two-stage nucleation model at 623, 648, 673, 698 and 723 K. The reaction rate is limited by the first nucleation stage rate (proton transition from an OH group near the reaction interface on a freed vacant orbital of an oxygen ion of the OH group in the nearest elementary cell, i.e., formation of a structured water molecule). The second-stage rate (water molecule removal from the structure and proton migration from the residual hydroxyl inside the structure) is about 1 order of magnitude higher. The activation energy of the limiting stage is 194 and 163 kJ mol^?1 for the original and irradiated samples, respectively. Non-linear Arrhenius dependencies for the first-stage rate constants are related to the potential barrier reduction due to thermal fluctuations of large structural zones (with radii of about 20 and 81 Å in original and irradiated samples, respectively), whose ions form this barrier.     

Ab initio 2-D periodic Hartree–Fock study of Fe-substituted lizardite 1T– a simplified cronstedtite model

 A 2-D periodic ab initio Hartree–Fock LCAO study was performed on Fe-substituted 1:1 sheet silicate, lizardite. The atomic orbitals were described by large-core pseudopotentials (Fe atoms) and a sp basis set (the other atoms). Calculated atomic charges and the results of bond population analysis indicate that the Fe-O bond was as ionic as the Mg-O. This hypothesis was supported by calculated density of states and electron density maps. Increasing Fe for Mg substitution changed the shape of projected density of states (PDOS) of O(p) orbitals. Received: 27 January 2000 / Accepted: 21 May 2000     

The nonlinear elasticity and related properties of anhydrous and hydrous γ-Mg2SiO4: a theoretical study

The second-order elastic constants up to 30 GPa, which encompass the stability field of the spinel forms, their pressure derivatives and the third-order elastic constants of both hydrous and anhydrous -Mg₂SiO₄ have been obtained theoretically. A combination of deformation theory and finite strain elasticity theory has been employed to arrive at the expressions for second-order and third-order elastic constants from the strain energy of the lattice. The strain energy is calculated by taking into account the interactions up to second nearest neighbours in the -Mg₂SiO₄ lattice. This is then compared with the strain-dependent lattice energy from continuum model approximation to obtain the expression of elastic constants. The second-order elastic constants C_ij compare favourably with the measurements in the case of anhydrous as well as hydrous -Mg₂SiO₄ and with other calculations on the anhydrous phase. All the third-order elastic constants of both the compounds are negative. The third-order elastic constant C₁₄₄(–52.41 and –45.07 GPa for anhydrous and hydrous -Mg₂SiO₄, respectively) representing the anisotropy of shear mode has a smaller value than C₁₁₁ (–2443.94 and –2101.25 GPa for anhydrous and hydrous phases, respectively), which corresponds to the longitudinal mode. The pressure-induced variations in the longitudinal elastic constants (i.e.,dC₁₁/dp) are relatively large (4.08 and 4.09 for dry and hydrous ringwoodite, respectively) compared with those for the shear (0.22 and 0.32 for dry and hydrous ringwoodite, respectively) and off-diagonal constants (1.40 and 1.41 for dry and hydrous ringwoodite, respectively). The variation of the shear moduli C_s and anisotropy factor A with pressure have also been studied. The average value of elastic anisotropy is 0.835 in the case of anhydrous -Mg₂SiO₄ and 0.830 in the hydrous phase. The reversal of sign of the Cauchy pressure C₁₂ – C₄₄, which describes the angular character of atomic bonding in metals and other compounds, at around 21 GPa for both the compounds may be a precursor to the phase transition from ringwoodite to periclase and perovskite at an elevated temperature. The aggregate elastic properties like the adiabatic bulk modulus K (175.4 and 150.2 GPa for anhydrous and hydrous phases, respectively), and the isotropic compressional (P) and shear (S) wave velocities were calculated and the mode Grüneisen Parameters (GPs) of the acoustic waves were determined based on the quasi-harmonic approximation. The low temperature limit of both hydrous and anhydrous phases of -Mg₂SiO₄ are positive (1.69 and 1.78, respectively, for hydrous and anhydrous phases) and hence we expect the thermal expansion to be positive down to absolute zero. The Anderson–Grüneisen parameter obtained for hydrous as well as anhydrous phases of -Mg₂SiO₄ from the second-order and third-order elastic constants are 2.30 and 2.29, respectively.     

Crustal structure of the Alpine–Pannonian transition zone: a combined seismic and gravity study

 The crustal structure of the transition zone between the Eastern Alps and the western part of the Pannonian depression (Danube basin) is traditionally interpreted in terms of subvertical Tertiary strike-slip and normal faults separating different Alpine tectonic units. Reevaluation of approximately 4000-km-long hydrocarbon exploration reflection seismic sections and a few deep seismic profiles, together with data from approximately 300 wells, suggests a different structural model. It implies that extensional collapse of the Alpine orogene in the Middle Miocene was controlled by listric normal faults, which usually crosscut Alpine nappes at shallow levels, but at depth merge with overthrust planes separating the different Alpine units. The alternative structural model was tested along a transect across the Danube basin by gravity model calculations, and the results show that the model of low-angle extensional faulting is indeed viable. Regarding the whole lithosphere of the western Pannonian basin, gravity modelling indicates a remarkable asymmetry in the thickness minima of the attenuated crust and upper mantle. The approximately 160 km lateral offset between the two minima suggests that during the Miocene extension of the Pannonian basin detachment of the upper crust from the mantle lithosphere took place along a rheologically weak lower crust. Received: 13 July 1998 / Accepted: 18 March 1999     

Experimental study of the mechanical and thermal properties of lignin fiber-stabilized loess under freeze-thaw cycles北大核心CSCD

冻融循环作用是造成寒区工程病害的主要因素之一。为探究冻融循环对木质素纤维改良黄土力学和热学的影响,通过轻型击实试验、冻融循环试验、不固结不排水三轴剪切试验、热常数分析试验和X射线衍射试验,以木质素纤维掺量、冻融循环次数和围压为变量展开研究。结果表明：随着掺量的增加,改良黄土的最大干密度降低,最优含水率升高;随着冻融循环次数的增加,试样的应力-应变曲线由应变硬化型向应变弱软化型转变;试样的质量损失率、破坏强度、弹性模量、黏聚力、内摩擦角和导热系数均随着冻融循环次数的增加呈下降趋势,在经历第1次冻融循环后衰减率最高,并且总是在掺量为5%时达到最大值;试样的破坏强度和黏聚力在经历6~9次冻融循环后趋于稳定;黄土及掺量为5%的改良黄土在X射线衍射分析中成分相似,未发现新的物质生成,因此,木质素纤维是一种绿色的物理固化材料。该研究成果可为寒区土体加固提供新思路。     

Effects of temperature on the crystal structure of epidote: a neutron single-crystal diffraction study at 293 and 1,070 K

The effects of temperature on the crystal structure of a natural epidote [Ca_1.925 Fe_0.745Al_2.265Ti_0.004Si_3.037O₁₂(OH), a = 8.890(6), b = 5.630(4), c = 10.150(6) Å and β = 115.36(5)°, Sp. Gr. P2₁ /m] have been investigated by means of neutron single-crystal diffraction at 293 and 1,070 K. At room conditions, the structural refinement confirms the presence of Fe³⁺ at the M₃ site [%Fe(M3) = 73.1(8)%] and all attempts to refine the amount of Fe at the M(1) site were unsuccessful. Only one independent proton site was located. Two possible hydrogen bonds, with O(2) and O(4) as acceptors [i.e. O(10)–H(1)···O(2) and O(10)–H(1)···O(4)], occur. However, the topological configuration of the bonds suggests that the O(10)–H(1)···O(4) is energetically more favourable, as H(1)···O(4) = 1.9731(28) Å, O(10)···O(4) = 2.9318(22) Å and O(10)–H(1)···O4 = 166.7(2)°, whereas H(1)···O(2) = 2.5921(23) Å, O(10)···O(2) = 2.8221(17) Å and O(10)–H(1)···O2 = 93.3(1)°. The O(10)–H(1) bond distance corrected for “riding motion” is 0.9943 Å. The diffraction data at 1,070 K show that epidote is stable within the T-range investigated, and that its crystallinity is maintained. A positive thermal expansion is observed along all the three crystallographic axes. At 1,070 K the structural refinement again shows that Fe³⁺ share the M(3) site along with Al³⁺ [%Fe(M3)_1,070K = 74(2)%]. The refined amount of Fe³⁺ at the M(1) is not significant [%Fe(M1)_1,070K = 1(2)%]. The tetrahedral and octahedral bond distances and angles show a slight distortion of the polyhedra at high-T, but a significant increase of the bond distances compared to those at room temperature is observed, especially for bond distances corrected for “rigid body motions”. The high-T conditions also affect the inter-polyhedral configurations: the bridging angle Si(2)–O(9)–Si(1) of the Si₂O₇ group increases significantly with T. The high-T structure refinement shows that no dehydration effect occurs at least within the T-range investigated. The configuration of the H-bonding is basically maintained with temperature. However, the hydrogen bond strength changes at 1,070 K, as the O(10)···O(4) and H(1)···O(4) distances are slightly longer than those at 293 K. The anisotropic displacement parameters of the proton site are significantly larger than those at room condition. Reasons for the thermal stability of epidote up to 1,070 K observed in this study, the absence of dehydration and/or non-convergent ordering of Al and Fe³⁺ between different octahedral sites and/or convergent ordering on M(3) are discussed.     

An XRD study of the crystal structure of gearksutite and its stability during heating to 300°C

The crystal structure of gearksutite, Ca and Al hydrofluoride CaAlF₄(OH) · H₂O, was refined using the Rietveld method with power diffraction data. The thermal stability of its crystal structure was studied for the first time using high-temperature XRD. Thermal XRD study of the mineral in the temperature range from 25 to 300°C revealed its stability to temperatures of 300-310°C. The mineral began to decay at temperatures greater than 300°C. The increase in the unit-cell parameters was established and the coefficients of thermal expansion were calculated.     

An anionic biopolymer γ-polyglutamate enhanced the microbially induced carbonate precipitation for soil improvement: mechanical behaviors and underlying mechanism

The use of biopolymer to improve the performance of microbially induced carbonate precipitation (MICP)-treated sands is a novel and eco-friendly concept. This work found an anionic biopolymer, γ-polyglutamate (γ-PGA), could significantly improve the performance of MICP-treated sands. Comparing the control with absence of γ-PGA, the concentration of 0.1–9 g/L γ-PGA increased the compressive strength of MICP-treated sands by 1.54–3.96 times and significantly reduced the brittleness. The MICP process analysis and microstructural detection demonstrated that γ-PGA in the specimens provided many nucleation sites and templates for calcite generation, partially kept the bacterial urease activity by replacement of the bacteria as nucleation sites, thereby improving the calcite generation. The γ-PGA also cemented sand grains with calcite through the hydrogen bond-type intermolecular interactions. Both the calcite generation and the hydrogen bond-type intermolecular interactions by γ-PGA played vital roles in enhancing MICP for soil improvement. Additionally, γ-PGA, as a viscoelastic admixture between the crystals and sand grains, effectively dissipated the energy of stress and thus reduced the brittleness of MICP-treated sands. This is the first report on the application of anionic biopolymer to MICP technology. It provides a novel concept in promoting the efficiency and sustainability of MICP.

     

Experimental study on mechanical properties and pore characteristics of the modified lime mortars under freee-thaw cycles北大核心CSCD

石灰土作为路基填料代替宕渣是一种较为经济的方案,但灰土初始强度低、硬化速率慢、碳化时间长,不利于快速施工,需要进行改良研究。利用偏高岭土与石灰发生火山灰反应的原理改良灰土,通过单轴压缩试验和三轴压缩试验,分析改良灰土冻融循环条件下力学参数变化规律,利用图像处理技术提取改良灰土图像表面孔隙,建立孔隙率与强度的关系,并通过研究龄期、石灰含量和含水率变化规律,分析偏高岭土改良灰土的机制。结果表明：偏高岭土能够有效提高灰土材料反应速率,改善灰土力学特性;偏高岭土在一定程度上能够恢复冻融循环导致的灰土力学性能损失,降低冰晶体产生的孔隙;灰土强度达到最优后,其强度随着石灰的增加而降低,而经偏高岭土改良后其强度将继续增加;火山灰反应比灰土碳化过程消耗更多的水分,有效提高了灰土的抗冻性能。     

Deep structure and volcanic activity of Mount Elbrus and a portion of the Elbrus–Tyrnyauz valley: Geological and geophysical data

Doklady Earth Sciences - A microseismic sounding profile was made along the Baksan River valley from the eastern summit of Elbrus volcano to the southern edge of town Tyrnyauz. The geological...     

Species composition and forest structure in tropical moist deciduous forest of Bangladesh—a case study in Thakurgaon

This study was conducted in the tropical moist deciduous forest in Bangladesh to describe the species composition, diversity, and the forest structure. There were three plots established in Ranishonkoil, Ruhia, and Baliadangi forest beat in Thakurgaon. A total of 126 tree species, 1,991 stems (663 ha^?1) of ≥10-cm girth were listed. Tree communities in these forest region differed in dominance, composition, diversity, and structure; and tree stand density varied from 651 to 685 ha^?1. Species diversity (H¹) ranges from 3.11 to 3.48. Meliaceae, Myrtaceae, and Rubiaceae were the most abundant families within the three plot area. Study site 2 is more diverse at spatial scale and taxonomic levels due to high rainfall and favorable edaphic condition. This study will help the foresters as baseline information for monitoring and sustaining diversity of tropical moist deciduous forests in Bangladesh.     

Ab initio crystal structure and elasticity of tuite, γ-Ca<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>, with implications for trace element partitioning in the lower mantle

Tuite forms by the breakdown of apatite at high pressure and is thus expected to play a role in extending the phosphorus cycle beyond the stability field of apatite and into the lower mantle. With its large, high-coordination cation sites, tuite is thought to be able to dissolve large quantities of incompatible elements such as rare earth elements, Sr, Th, and U, and is potentially an important mantle reservoir for these elements. In this paper, ab initio calculations of the structure and elasticity of tuite to lower mantle pressure are presented and used to probe trace element incorporation. The calculated zero-pressure volumes of the M1 and M2 cation sites were 50.23 and 36.61 Å³, while the corresponding bulk moduli K ₀ are 116.1 and 94.2 GPa, significantly lower than the 234.1 GPa calculated for the M site of CaSiO₃ perovskite (cpv), another likely host for incompatible elements in the mantle. The partitioning of impurities between tuite and cpv is investigated using a lattice strain model, parameterized by the ab initio calculations, to calculate isovalent substitution energies across a range of pressures and impurity sizes. Additionally, energies of strontium and barium defects in tuite are compared with those of equivalent defects in cpv, and it is found that both elements will partition strongly from cpv into tuite.     

Comment: A study of “probabilistic” and “deterministic” geostatistics

Stochastic process theory involves integrals of measurable functions over probability measure spaces. One of these is the ensemble space, Ω, whose members are sample functions on Euclidean spaceR ^k and the other isR ^k itself. What geostatisticians call the “theory of regionalized variables” is said to based on stochastic theory. A recent paper inMathematical Geology proclaims a distinction between “probabilistic” and “deterministic” geostatistics. The former is said to rely on “ensemble integrals” over Ω and the latter on “spatial integrals” overR ^k. This study shows that the proposed distinction rests on an arbitrary choice between two estimators for the covariance of a stochastic process; neither is an ensemble integral, both are spatial integrals, and both are Kolmogorov inconsistent. The “deterministic” estimator is identical with that of classical bivariate least-squares regression in which “spatial structure” is of no consequence. This study shows that both stochastic models are suboptimal approximations to the unique nonstationary classical statistical multivariate regression model generated by each sample pattern. The stochastic process model and its “spatial continuity measures,” thus, appear as questionable mathematical embellishments on suboptimal estimates, correspondence with geomorphic reality is tenuous, and estimates are biased and distorted. Various related misconceptions in the paper are also discussed.     

Integration of GIS and remote sensing for estimation of soil loss and prioritization of critical sub-catchments: a case study of Tapacurá catchment

Mapping of erosion risk areas is an important tool for the planning of natural resources management, allowing researchers to propose the modification of land use properly and implement more sustainable long-term management strategies. The objective of this study was to assess and identify critical sub-catchments for soil conservation management using the USLE, GIS, and remote sensing techniques. The Tapacurá catchment is one of the planning units for water resource management of the Recife Metropolitan Region. Maps of the erosivity (R), erodibility (K), slope (LS), cover-management (C), and support practice (P) factors were derived from the climate database, digital elevation model, and soil and land-use maps. In order to validate the simulation process, total sediment delivery ratio was estimated. The results showed a mean sediment delivery ratio (SDR) of around 11.5?% and a calculated mean sediment yield of 0.108?t?ha^?1?year^?1, which is close to the observed one, 0.169?t?ha^?1?year^?1. The obtained soil loss map could be considered as a useful tool for environmental monitoring and water resources management. The methodology applied showed acceptable precision and allowed the identification of the most susceptible areas to soil erosion by water, constituting an important predictive tool for soil and environmental management in this region, which is highly relevant for the prediction of varying development scenarios for Tapacurá catchment. This approach can be applied to other areas for simple and reliable identification of critical areas of soil erosion in catchments.     

Geological structure and isotopic—geochronologic study of rocks from the Strel’na segment of the Terskii Greenstone belt,Kola Peninsula

The geological structure, age, and genesis of sedimentary—volcanogenic, metamorphic, and metasomatic rocks from the Terskii greenstone belt fringing the southern Imandra—Varzuga structure in the southeastern Kola Peninsula are discussed with defining main stages in endogenic activity of the region in the Late Archean and Early Proterozoic. The U-Pb method (SHRIMP-II, ID-TIMS, and Pb-LS techniques) was used to determine the age of volcano-sedimentary rocks of the Imandra Group as well as that of magmatic and superimposed metamorphic and metasomatic processes. The basic—intermediate metavolcanics of the Imandra Group are dated at 2.67 Ga, which corresponds to the Lopingian Gimol’skii Superhorizon (Late Archean). The Archean metavolcanics were subjected to Early Proterozoic regional metamorphism 2.1 Ga ago and metasomatic processes in the period of 1.85 to 1.77 Ga ago. The obtained data indicate multistage evolution of rock formation in the Terskii greenstone belt located in the southern flank of the Imandra—Varzuga structure in the Kola Peninsula.     

Thermal infrared (vibrational) spectroscopy of Mg–Fe olivines: A review and applications to determining the composition of planetary surfaces

The reststrahlen features in thermal infrared, or vibrational, spectra of Mg-Fe olivines ((Mg,Fe)₂SiO₄) exhibit trends in position, strength, and number of features that are diagnostic of the relative proportions of the Mg and Fe cations in the minerals. Although band positions move to lower wavenumbers (longer wavelengths) across the forsterite–fayalite compositional binary in a generally linear manner, specific feature shifts in transmittance data are described best by two linear fits with a break in slope near Fo₇₀. The break in slope may be accompanied by an offset as well; both traits are attributed to structural changes in olivine brought about by distortion of the crystal lattice by Fe. Reflectance and emissivity spectra exhibit similar trends in band position with composition, and all three types of data demonstrate that some olivine band strengths change across the Mg–Fe solid solution series and also are diagnostic of composition. Olivines have been identified in a wide array of thermal infrared spectra of planetary materials and have been interpreted as being present on the surfaces of Mercury, the Moon, Mars, and a number of asteroids based on the analysis of thermal infrared spectra. New linear least squares models of the emissivity spectra of olivine-bearing Martian meteorites enable a preliminary estimation of the accuracy with which quantitative estimates of olivine abundance and solid solution composition can be derived from the spectra of mixtures.     

An experimental study of dissolution–reprecipitation in fluorapatite: fluid infiltration and the formation of monazite

In a series of timed experiments, monazite inclusions are induced to form in the Durango fluorapatite using 1 and 2 N HCl and H₂SO₄ solutions at temperatures of 300, 600, and 900°C and pressures of 500 and 1,000 MPa. The monazite inclusions form only in reacted areas, i.e. depleted in (Y+REE)+Si+Na+S+Cl. In the HCl experiments, the reaction front between the reacted and unreacted regions is sharp, whereas in the H₂SO₄ experiments it ranges from sharp to diffuse. In the 1 N HCl experiments, Ostwald ripening of the monazite inclusions took place both as a function of increased reaction time as well as increased temperature and pressure. Monazite growth was more sluggish in the H₂SO₄ experiments. Transmission electron microscopic (TEM) investigation of foils cut across the reaction boundary in a fluorapatite from the 1 N HCl experiment (600°C and 500 MPa) indicate that the reacted region along the reaction front is characterized by numerous, sub-parallel, 10–20 nm diameter nano-channels. TEM investigation of foils cut from a reacted region in a fluorapatite from the 1 N H₂SO₄ experiment at 900°C and 1,000 MPa indicates a pervasive nano-porosity, with the monazite inclusions being in direct contact with the surrounding fluorapatite. For either set of experiments, reacted areas in the fluorapatite are interpreted as replacement reactions, which proceed via a moving interface or reaction front associated with what is essentially a simultaneous dissolution–reprecipitation process. The formation of a micro- and nano-porosity in the metasomatised regions of the fluorapatite allows fluids to permeate the reacted areas. This permits rapid mass transfer in the form of fluid-aided diffusion of cations to and from the growing monazite inclusions. Nano-channels and nano-pores also serve as sites for nucleation and the subsequent growth of the monazite inclusions.