Thermochemistry of sulfide liquids IV: density measurements and the thermodynamics of O–S–Fe–Ni–Cu liquids at low to moderate pressures

We present the results of a series of density experiments in the system O–S–Fe–Ni–Cu. These experiments were designed to extend our understanding of the physical properties of sulfide liquids, and to extend one-bar thermochemical models for sulfide liquids to apply to low to moderate pressures. Density measurements indicate both positive and negative deviations from linear mixing of partial molar volumes across this five-dimensional composition space. In terms of the homogeneous speciation model of Kress (in Contrib Mineral Petrol 154:191–204, 2007), the best fit to experimental data can be achieved by starting with a model where the volume of formation reaction for associated species initially is set to zero. Further refinement of this first-order fit yields a volume mixing model which reproduces experimental data to within nearly the estimated experimental uncertainty. Experimental ultrasonic and X-ray absorption data from the literature, along with the bulk modulus–volume relation of Anderson and Nafe (J Geophys Res 16:3951–3963, 1965), allow the estimation of the pressure dependence of partial molar volumes for sulfide liquid species. The resulting combined thermochemical model should be valid to about 2,000 K and 3 GPa. Application of this thermochemical model in a simple adiabatic magma ascent scenario confirms earlier work suggesting that the pressure dependence of sulfur solubility in sulfide-saturated magma will decrease with increasing pressure along geologically reasonable paths in P–T–– space.     

Explicit extension of the p–y method to pile groups in sandy soils

The method of “p–y” curves has been extensively used, in conjunction with simplified numerical methods, for the design and response evaluation of single piles. However, a straightforward application of the method to assess the response of pile groups is questionable when the group effect is disregarded. For this reason, the notion of p-multipliers has been therefore introduced to modify the “p–y” curves and account for pile group effect. The values proposed for p-multipliers result from pile group tests and are limited to the commonly applied spacing of 3.0 D and layout less than 3 × 3, restricting the applicability of the method to specific cases. With the aim of extending the applicability of the “p–y” method to pile groups, the authors have already proposed a methodology for estimating the “p _G–y _G” curves of soil resistance around a pile in a group for clayey soils. A complementary research allowing for the estimation of the “p _G–y _G” curves for sandy soils is presented in this paper. The well-known curves of soil resistance around the single pile in sandy soils are appropriately transformed to allow for the interaction effect between the piles in a group. Comparative examples validate the applicability and the effectiveness of the proposed method. In addition, the method can be straightforwardly extended to account for varying soil resistance, according to the particular location of a pile in a group. It can therefore be used in a most accurate manner in estimating the distribution of forces and bending moments along the characteristic piles of a group and therefore to design a pile foundation more accurately.     

Explicit extension of the p–y method to pile groups in cohesive soils

Although simplified numerical methods are reliable for evaluating the response of a single pile under horizontal load, their application is questionable for assessing the response of pile groups. The notion of “p–y” curves has been considered with the aim of establishing a transformation relationship able to provide the “p_G–y_G” curves of soil resistance around a pile in a group from the well-known curves of soil resistance around the single pile.This transformation extends the applicability of the “p–y” method to pile groups, without the need for time consuming numerical computations, rendering the proposed method efficient and attractive. Comparative examples demonstrated the applicability and the effectiveness of the proposed method. In addition, the method can be straightforwardly extended to account for varying soil resistance, according to the particular location of a pile in a group. It can therefore be used to estimate accurately force and bending moment distributions along the characteristic piles of a group, which are required for the efficient design of foundations.     

Strain and local heterogeneity in the forsterite–fayalite solid solution

Infrared powder-absorption spectra of nine natural and five synthetic olivine samples across the forsterite–fayalite join have been investigated at room temperature in the range 70–1400 cm^–1. Variations of peak positions as a function of Fe content are close to linear for those vibrational bands whose trend could be followed across the solid solution. Line-broadening has been quantified by autocorrelation analysis. Positive deviations from linearity of the line-broadening parameter, _corr, for groups of bands at low energies are consistent with the existence of local elastic strain heterogeneities at intermediate compositions in the solid solution. It also appears that the structure of forsterite is more homogeneous than Fe-rich olivines in relation to local elastic strain effects. Positive deviations from linearity of the line-broadening parameter for the low-energy regions scale linearly with calorimetric data for the enthalpy of mixing. This close correlation between line-broadening in IR spectra and calorimetric enthalpies of mixing has now been observed for four different binary solid solutions, and there is a further, qualitative correlation with bulk modulus.     

Heavy metal contamination of soils and waters in and around the Imcheon Au–Ag mine,Korea

The heavy metal contamination of soils and waters by metalliferous mining activities in an area of Korea was studied. In the study area of the Imcheon Au–Ag mine, soils and waters were sampled and analyzed using AAS for Cd, Cu, Pb and Zn. Analysis of HCO₃⁻, F⁻, NO₃⁻ and SO₄²⁻ in water samples was also undertaken by ion chromatography. Elevated concentrations of the metals were found in tailings. The maximum contents in the tailings were 9.4, 229, 6160 and 1640 mg/kg extracted by aqua regia and 1.35, 26.4, 70.3 and 410 mg/kg extracted by 0.1 N HCl solution for Cd, Cu, Pb and Zn, respectively. These metals are continuously dispersed downstream and downslope from the tailings by clastic movement through wind and water. Because of the existence of sulfides in the tailings, a water sample taken on the tailings site was very acidic with a pH of 2.2, with high total dissolved solids (TDS) of 1845 mg/l and electric conductivity (EC) of 3820 μS/cm. This sample also contained up to 0.27, 1.90, 2.80, 53.4, 4,700 mg/l of Cd, Cu, Pb, Zn and SO₄²⁻, respectively. TDS, EC and concentrations of metals in waters decreased with distance from the tailings. The total amount of pulverized limestone needed for neutralizing the acid tailings was estimated to be 46 metric tons, assuming its volume of 45,000 m³ and its bulk density of 1855 kg/m³.     

Influence of geological setting on geochemical baselines of trace elements in soils. Application to soils of South–West Spain

A collection of 235 samples were taken from 115 sites (representing a density of 1 sampling site ca. 130 km²) on rural soils derived from the major rock types in the southern Iberian Massif. The geochemical baselines of selected trace elements (As, Co, Cr, Cu, Ni, Pb and Zn) were determined on the < 2 mm soil fraction. The sampling sites were not directly influenced by external pollution. Soil geochemical baseline and threshold values were calculated for each element in two geologically different zones: the Ossa-Morena Zone (OMZ) and the South-Portuguese Zone (SPZ).     

The effect of sulfur content on density of the liquid Fe–S at high pressure

The density of liquid Fe–S was measured at 4 GPa and 1,923 K using a sink/float method with a composite density marker. The density marker consisted of a Pt rod core and an Al₂O₃ tube surrounding. The uncertainty in the density of the composite marker is much smaller than that of the composite sphere, which had been used in previous density measurements. The density of liquid Fe–S decreases nonlinearly with increasing sulfur content at 4 GPa and 1,923 K. This tendency is consistent with the results measured at ambient pressure. The molar volume of FeS calculated from the measured density gradually increases with sulfur content. The excess molar volume from ideal mixing of Fe and S at 4 GPa was negative value. The new method proposed here is applicable to the density measurement of other Fe alloys at high pressure. The tendency of the molar volume and the excess molar volume with sulfur content at ambient pressure is consistent with these at high pressure at least up to 4 GPa. The excess molar volume at high pressure is essential for estimating the amount of light elements in the outer core.     

Assessment to the potential mobility and toxicity of metals and metalloids in soils contaminated by old Sb–Au and As–Au mines (NW Portugal)

The main purpose of this study is to assess arsenic and antimony availability in soils, as well as Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn availability in soils derived from the schist–metagraywacke complex close to old Sb–Au mines and in soils developed from Ordovician slates and close to an old As–Au mine in Portugal. The availability was determined using a European certified sequential extraction procedure (BCR). The results demonstrated that metalloids are not readily bioavailable, because they are mainly associated with the residual fraction. Arsenic and antimony proportions in exchangeable fractions are up to 3 and 1%, respectively. However, arsenic is up to 24% in oxy-hydroxide fractions, while antimony is up to 4% in them, demonstrating the highest bioavailability of arsenic compared to that of antimony, as metalloids are weakly bound to the soils in that fraction. Therefore, arsenic tends to be more toxic than antimony in all soils studied. However, the pseudo-total contents show that both metalloids are above the Italian and Dutch guidelines. Therefore, if physico-chemical changes occur arsenic and antimony will show higher potential environmental risk than evidenced by Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn.     

The role of water resources in the evolution of the Israeli–Lebanese border

The current location of the border between Lebanon and Palestine, today's Israel, is a product of various competing forces. The Zionist Organization aspired to include the entire Galilee region up to the lower reaches of the Litani River (also known as the Kassimiyah River) within Palestine. The river itself was the desired northern border of the country. The Zionists supported their position by employing instrumental arguments that were largely related to the availability of water resources. On the other hand, residents of the upper Galilee, today's southern Lebanon, demanded that they be included with Lebanon. They used their trade links with Beirut, and cultural and familial ties with other parts of Lebanon to support their position. These instrumental and expressive arguments appear to have assisted in the demarcation of the border between Lebanon and Palestine. Currently, access to the water resources, not necessarily control over them, is likely to influence negotiations between Israel and Lebanon over the future of the Israeli-occupied security zone in southern Lebanon.     

Determining the composition of C–H–O liquids following high-pressure and high-temperature diamond-trap experiments

Here, we present the first analytical technique (the quartz tube system technique—QTS) to directly analyze H₂O and CO₂ contents in liquids following high-pressure, high-temperature experiments in capsules containing mantle minerals and a diamond layer serving as a fluid/melt trap. In this technique, the capsule is frozen prior to opening; the diamond trap is cut out of the capsule and placed inside a N₂-filled quartz tube. The diamond trap is heated up to 900 °C to release the gases to an Infrared Gas Analyzer, which determines the CO₂ and H₂O contents. Three sets of experiments containing SiO₂ and CaCO₃ powders were performed at 6 GPa and 1,000 °C in order to calibrate and validate the technique. These experiments demonstrated that when samples are prepared in a N₂ environment, CO₂ and H₂O can be directly measured with an accuracy and precision of 2–3 and 3–4 %, respectively. The QTS technique (for H₂O and CO₂ determination) together with the cryogenic technique (total dissolved solids content) can be applied to diamond-trap capsules following HP–HT experiments in order to provide direct and complete liquid compositions coexisting with mantle material. The principal advantage of the QTS technique of direct analysis of volatile content in liquids over the indirect approach of mass balance calculations is the possibility of studying carbonated and hydrous liquid compositions in equilibrium with mantle material regardless of chemistry and pressure–temperature experimental conditions.     

Gravitational interactions of the solid core and the Earth’s mantle and variations in the length of the day

A simple mechanical model explaining the long-period (about 100-year) variations in the Earth’s rotational velocity is proposed. This model takes into account the gravitational interaction of the mantle with the solid core of the Earth and the fact that the core rotation leads that of the mantle. Well-known Earth parameters provide estimates of the gravitational torque that support the proposed model. The mathematical problem involved reduces to the classical problem of a nonlinear oscillator exposed to a constant torque. The well-known parameters of the core-mantle system result in a stable equilibrium and a stable limiting cycle on the phase cylinder of this oscillator. This equilibrium corresponds to a single angular velocity for the mantle and solid core, with no long-period oscillations in the length of the day. The limiting cycle corresponds to the core rotation leading the mantle rotation. In this case, the ellipsoidality of the gravitationally interacting bodies provides a periodic interchange of kinetic angular momentum between the mantle and solid core that results in long-period variations in the length of the day. The proposed model does not support the formerly widespread opinion that the core rotates more slowly than the mantle.     

Effect of the soil–pile–structure interaction in seismic analysis: case of liquefiable soils

The design of earthquake-resistant structures depends greatly on the soil–foundation–structure interaction. This interaction is more complex in the presence of liquefiable soils. Pile and rigid inclusion systems represent a useful practice to support structures in the presence of liquefiable soils in seismic zones. Both systems increase the bearing capacity of soil and allow reducing the settlements in the structure. Numerical models with a 3-storey reinforced concrete frame founded on inclusions systems (soil–inclusion–platform–structure) and pile systems (soil–pile–structure) were analyzed. Finite difference numerical models were developed using Flac 3D. Two different soil profiles were considered. A simple constitutive model for liquefaction analysis that relates the volumetric strain increment to the cyclic shear strain amplitude was utilized to represent the behavior of the sand, and the linear elastic perfectly plastic constitutive model with a Mohr–Coulomb failure criterion was used to represent the behavior of the earth platform. Two earthquakes were used to study the influence of the different frequency of excitation in the systems. The results were presented in terms of maximum shear forces distribution in the superstructure and spectrum response of each system. The efforts and displacements in the rigid elements (piles or rigid inclusions) were compared for the different systems. The bending and buckling failure modes of the pile were examined. The results show that the pile system, the soil profile and the frequency of excitation have a great influence on the magnitude and location of efforts and displacements in the rigid elements.

     

On the way to a better state? The role of NGOs in the planning and implementation of protected areas in Brazil

Protected areas are considered some of the most versatile as well as important instruments of nature conservation and environmental policies. The `classic' model of nature conservation aims at the isolation of large areas in order to preserve their `pristine' nature from human interference. However, the transfer of this model to developing countries led to serious conflicts with local people. From a socio-geographical viewpoint, protected areas can be understood as regulative tools for the shaping and controlling of space. This approach helps to recognise the influence of distinct modes of appropriation of space and nature on the emergence and course of conflicts. In the present article it is used to analyse the leading role played by Brazilian NGOs in the transformation of the classic model of protected area management at the beginning of the nineties. Two case studies – dealing with the implementation of the Amazonian Mamirauá Reserve and with the reform of the Brazilian protected area legislation – are used to illustrate not only the success of the new approaches, but also the expectations and contradictions which surround the future development of protected areas in Brazil.     

Laboratory investigation and constitutive modeling of the mechanical behavior of sand–GRP interfaces

Acta Geotechnica - The frictional behavior of soil–pipe interfaces plays a paramount role in the design and construction of underground pipes, particularly applying trenchless technologies...     

A method for estimating the activity of titania in magmatic liquids from the compositions of coexisting rhombohedral and cubic iron–titanium oxides

A method is described for estimating the activity of titania (TiO₂) in a magmatic liquid from the compositions of coexisting cubic oxide (spinel) and rhombohedral oxide (ilmenite). These estimates are derived from the thermodynamic models of Ghiorso and Evans (Am J Sci 308:957–1039, 2008; see also Sack and Ghiorso in Contrib Mineral Petrol 106:474–505, 1991a; Am Mineral 76:827-847, 1991b) and may be computed self consistently along with temperature and oxygen fugacity for an assumed pressure. The method is applied to a collection of 729 naturally occurring oxide pairs from rhyolites and dacites. For this suite of oxides, values of titania activity relative to rutile saturation range from 0.3 to 0.9. Genetically related groups of oxide pairs display activity–temperature trends with negative slopes at higher activities (0.6–0.9) or positive slopes at lower activities (0.3–0.7). Thermodynamic analysis supports the assumption of two-oxide, liquid equilibrium for the former group, but suggests that such an interpretation for oxide sequences with positive activity–temperature trends may be problematic. Application of the estimation method to oxide pairs from the Shiveluch Volcano and the Bishop Tuff reveals that the former are consistent with having equilibrated with known matrix glass compositions, whereas the latter pairs are inconsistent with equilibration with pre-eruptive liquids trapped in quartz inclusions.     

Sedimentary Evolution of the Qinghai–Tibet Plateau in Cenozoic and its Response to the Uplift of the Plateau

We have studied the evolution of the tectonic lithofacies paleogeography of Paleocene–Eocene, Oligocene, Miocene, and Pliocene of the Qinghai–Tibet Plateau by compiling data regarding the type, tectonic setting, and lithostratigraphic sequence of 98 remnant basins in the plateau area. Our results can be summarized as follows. (1) The Paleocene to Eocene is characterized by uplift and erosion in the Songpan–Garzê and Gangdisê belts, depression (lakes and pluvial plains) in eastern Tarim, Qaidam, Qiangtang, and Hoh Xil, and the Neo-Tethys Sea in the western and southern Qinghai–Tibet Plateau. (2) The Oligocene is characterized by uplift in the Gangdisê–Himalaya and Karakorum regions (marked by the absence of sedimentation), fluvial transport (originating eastward and flowing westward) in the Brahmaputra region (marked by the deposition of Dazhuka conglomerate), uplift and erosion in western Kunlun and Songpan–Garzê, and depression (lakes) in the Tarim, Qaidam, Qiangtang, and Hoh Xil. The Oligocene is further characterized by depressional littoral and neritic basins in southwestern Tarim, with marine facies deposition ceasing at the end of the Oligocene. (3) For the Miocene, a widespread regional unconformity (ca. 23 Ma) in and adjacent to the plateau indicates comprehensive uplift of the plateau. This period is characterized by depressions (lakes) in the Tarim, Qaidam, Xining–Nanzhou, Qiangtang, and Hoh Xil. Lacustrine facies deposition expanded to peak in and adjacent to the plateau ca. 18–13 Ma, and north–south fault basins formed in southern Tibet ca. 13–10 Ma. All of these features indicate that the plateau uplifted to its peak and began to collapse. (4) Uplift and erosion occurred during the Pliocene in most parts of the plateau, except in the Hoh Xil–Qiangtang, Tarim, and Qaidam.     

Kinematic analysis of Jurassic grabens of soulthern Turgai and the role of the Mesozoic stage in the evolution of the Karatau–Talas–Ferghana strike-slip fault,Southern Kazakhstan and Tian Shan

The Karatau–Talas–Ferghana Fault (KTF) extending for 1500 km from Turgai to western Tarim is one of the world’s largest intracontinental strike-slip faults. This paper overviews the evolution of the KTF, providing insight into its relatively poorly studied northern segment in the Karatau Range and Turgai, known as the Main Karatau Fault (MKF). The right-lateral strike-slip along the KTF developed during three stages in the late Permian–Triassic, Early–Middle Jurassic, and late Cenozoic. The total strike-slip decreases northward from 200 km in the Ferghana Range to 100 km in the Karatau Range and decreases to zero in southern Turgai. Kinematic analysis of Jurassic grabens compensating the strike-slip in southern Turgai shows that strike slip along the KTF in the Jurassic, previously regarded as insignificant, actually measures tens of kilometers and 50% of the total strike slip in the northern segment of this fault.