Partition of magnesium and iron between Olivine and spinel,and between pyroxene and spinel

Partition of Fe²⁺ and Mg between coexisting (Mg, Fe)₂SiO₄ spinel and (Mg, Fe)SiO₃ pyroxene was investigated at pressures 80 and 90 kbar and at temperatures 840 and 1050° C, using tetrahedral-anvil type of high pressure apparatus. Olivine-spinel solid solution equilibria in the system Mg₂SiO₄-Fe₂SiO₄ were discussed in the light of the partition reaction. Partition of Fe²⁺ and Mg in both olivine-spinel and pyroxene-spinel systems can not be regarded as that between ideal solid solutions. By applying the simple solution model for the partition of Fe²⁺ and Mg, sign of the heat of mixing was estimated to be positive for all olivine, spinel and pyroxene. Relative concentration of Fe²⁺ in spinel in the pyroxene-spinel system is likely to cause some change in the chemical composition of modified spinel () or spinel () in the transition zone of the mantle. A considerable change is also expected in the transition pressure of to ( + ) and ( + ) to .Presented at the symposium Recent Advances in the Studies of Rocks and Minerals at High Pressures and Temperatures held in Montreal, 1972. Jointly sponsored by the International Mineralogical Association and the Commission on Experimental Petrology.     

Allochthonous and autochthonous organic matter in natural waters: Kinetic and thermodynamic patterns of transformation and quantitative and qualitative compositions

Using adsorption of organic matter (OM) on diethylaminoethyl cellulose (DEAE-cellulose) in the dynamic mode, OM is divided into autochthonous and allochthonous. Based on the experiments on BOD kinetics and OM division into components, the kinetic parameters of autochthonous and allochthonous OM transformation are established for the first time (k_aut = 0.013, k_all = 0.0013 day^–1 at t =20°C). The activation parameters of transformation for autochthonous OM (ΔH^# = 75.6 kJ/mol, ΔS^# =–116.5 J/(mol K), and ΔG^# = 108.3 J/mol) and allochthonous OM (ΔH^# = 66.1 kJ/mol, ΔS^# =–149.1 J/(mol K), and ΔG^# = 108.0 J/mol) are calculated by the Arrhenius equation.

     

Chemical and Isotopic Characters of the Water and Suspended Particulate Materials in the Yellow River and Their Geological and Environmental Implications

The chemical and isotopic characteristics of the water and suspended particulate materials(SPM)in the Yellow River were investigated on the samples collected from 29 hydrological monitoring stations in the mainstem and several major tributaries during 2004 to 2007.TheδD andδ~(18)O values of the Yellow River water vary in large ranges from-32‰to-91‰and from-3.1‰to-12.5‰,respectively.The characters of H and O isotope variations indicate that the major sources of the Yellow River water are meteoric water and snow melting water,and water cycle in the Yellow River basin is affected strongly by evaporation process and human activity.The average SPM content(9.635g/L)of the Yellow River is the highest among the world large rivers.Compared with the Yangtze River,the Yellow River SPM has much lower clay content and significantly higher contents of clastic silicates and carbonates.In comparison to the upper crust rocks,the Yellow River SPM contains less SiO_2,CaO,K_2O and Na_2O,but more TFe_2O_3,Co,Ni,Cu,Zn,Pb and Cd.The abnormal high Cd contents found in some sample may be related to local industrial activity.The REE contents and distribution pattern of the Yellow River SPM are very close to the average value of the global shale.The averageδ~(30)Si_(SPM)in the Yellow River(-0.11‰)is slightly higher than the average value(-0.22‰)of the Yangtze River SPM.The major factors controlling theδ~(30)Si_(SPM)of the Yellow River are the soil supply,the isotopic composition of the soil and the climate conditions.The TDS in the Yellow River are the highest among those of world large rivers.Fair correlations are observed among Cl~-,Na~+,K~+,and Mg~(2+)contents of the Yellow River water,indicating the effect of evaporation.The Ca~(2+)and Sr~(2+)concentrations show good correlation to the SO_4~(2-)concentration rather than HCO_3~-concentration,reflecting its origin from evaporates.The NO_3~-contents are affected by farmland fertilization.The Cu,Zn and Cd contents in dissolved load of the Yellow River water are all higher than those of average world large rivers,reflecting the effect of human activity.The dissolved load in the Yellow River water generally shows a REE distribution pattern parallel to those for the Yangtze River and the Xijiang River.Theδ~(30)Si values of the dissolved silicon vary in a range from 0.4‰to 2.9‰,averaging1.34‰.The major processes controlling the D_(Si)andδ~(30)Si_(Diss)of the Yellow River water are the weathering process of silicate rocks,growth of phytolith in plants,evaporation,dissolution of phytolith in soil,growth of fresh water diatom,adsorption and desorption of aqueous monosilicic acid on iron oxide and human activities.The averageδ~(30)Si_(Diss)value of the Yellow River is significantly lower than that of the Nile River,Yangtze River and Siberia rivers,but higher than those of other rivers,reflecting their differences in chemical weathering and biological activity.Theδ~(34)S_(SO4)values of the Yellow River water range from-3.8‰to 14.1‰,averaging 7.97‰.There is some correlation between SO_4~(2-)content andδ~(34)S_(SO4).The factors controlling theδ~(34)S_(SO4)of the Yellow River water are the SO_4 in the meteoric water,the SO_4 from gypsum or anhydrite in evaporite rocks,oxidation and dissolution of sulfides in the mineral deposits,magmatic rocks and sedimentary rocks,the sulfate reduction and precipitation process and the sulfate from fertilizer.The~(87)Sr/~(86)Sr ratios of all samplesrange from 0.71041 to 0.71237,averaging 0.71128.The variations in the~(87)Sr/~(86)Sr ratio and Sr concentration of river water are primarily caused by mixing of waters of various origins with different~(87)Sr/~(86)Sr ratios and Sr contents resulting from water-rock interaction with different rock types.     

Impact and comminution processes in soft and hard rock

SummaryZertrümmerung von harten und weichen Felsen Eine experimentelle Untersuchung der Zertrümmerung von harten und weichen Felsen, nämlich grüner Tonschiefer und Diorit unter stoßartiger Belastung von Stahlkugeln mit 6,35 mm Durchmesser und von gewöhnlicher Munition wurde ausgeführt. Laborprüfungen mit Scheiben beider Materialen von 140 mm Durchmesser und unterschiedlichen Dicken wurden mit Kugeln durchgeführt im Geschwindigkeitsbereich von 50–260 m/s mittels einer Gasdruckkanone und für 340–2500 m/s mittels einer Pulverkanone. Geländeprüfungen an senkrechten Felsklippen aus Tonschiefer, ausgegraben in einem offenen Bergwerk, wurden durch Feuern von 20- und 40-mm-Geschossen mit Geschwindigkeiten von 610–880 m/s vorgenommen.Größe und Verteilung der Bruchstücke der verschiedenen Ziele wurden gemessen und die Geschwindigkeit gewisser Splitter wurde fotografisch bestimmt. Die Dimensionen der Krater und Höhlungen, erzeugt durch die Geschoßflugbahn, wurden bestimmt; plastische Verformung des Tonschiefers war in manchen Fällen vorhanden. In den ersten Versuchsreihen wurde auch die auf ein ballistisches Pendel übertragene Energie gemessen. Man bemühte sich, die Energie der durch den Stoß erzeugten Wellen in den Dioritscheiben zu messen, welches eine speziell zusammengesetzte, mit Dehnungsmeßstreifen ausgestattete Probe verlangte. Das Rißmuster auf einem diametralen Schnitt, verdeutlicht durch eine Farbflüssigkeit, wurde fotografisch vergrößert und vermessen.Man fand, daß in einem Bereich von sechs Dekaden der Schlagenergie die Tiefe des Loches im Tonschiefer eine gute Korrelation sowohl zu Anfangsimpuls als auch zu Anfangsenergie zeigte, und daß das Phänomen gut durch ein rein viskoses Ziel modelliert werden konnte. Die Zertrümmerungsenergie, welche die Differenz zwischen Anfangsenergie der Kugel und gemessenen Energien der Wellen im Ziel, Abprall der Kugel und Bewegung der Bruchteile ist, erreichte eine Größenordnung von 70–85 Prozent. Für die zur Bildung neuer Rißflächen benötigte Energie konnten wegen der Unsicherheit in der Bestimmung dieser Flächen nur obere und untere Grenzen ermittelt werden. Obwohl die Oberfläche der Ausbruchteile aus der gemessenen Größenverteilung und ihrer Gestalt, welche nur von einer Dimension abhing, bestimmt wurde, ist es nötig, die augenblickliche Forschung noch viel weiter zu treiben um eine komplette Analyse des Zerkleinerungs- und Ausstoßungsprozesses zu gewinnen.

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ZusammenfassungImpact and Comminution Processes in Soft and Hard Rock An experimental investigation was conducted to study the fragmentation of soft and hard rock, green shale and diorite, under conditions of impact by 6.35-mm (1/4-in.) diameter steel spheres and standard ammunition. Laboratory tests were conducted with the spheres at velocities from 50–260 m/sec (160–860 ft/sec) using a compressed gas gun and at speeds ranging from 340–2500 m/sec (100–8500 ft/sec) produced by a powder gun on 140-mm (5.5-in.) diameter disks of various thicknesses of both rocks. Field tests were also conducted with 20 and 40 mm ammunition fired at velocities in the range from 610–880 m/sec (2000–2900 ft/sec) against the excavated vertical green shale walls of a large open pit mine.Information has been collected on the size and distribution of the fragments dislodged from the various targets, and by means of photographic techniques, of the velocity of some of the ejecta. Crater and penetrating hole measurements have been performed and the compaction of the shale was noted in some instances. The energy transferred to a ballistic pendulum initially employed in the tests was determined. A major effort was exerted to measure the energy contained in the waves generated by impact in the diorite disks, involving a specially sectioned and straingaged composite sample; the crack pattern on a diametral section, delineated with the aid of a dye penetrant, was observed with suitable enlargement.It was found that, over a range of six decades of energy of the striker, the penetration depth in shale scaled reasonably well with both initial momentum and initial energy, and that the phenomenon could be satisfactorily modeled by a purely viscous target material. The energy of comminution for diorite, consisting of the difference between initial striker energy and the measured energies due to waves in the target, rebound of the projectile and motion of the ejecta was found to be of the order of 70 to 85 percent. Only upper and lower bounds could be established for the energy required to produce unit new surface in this event due to uncertainties in the establishment of crack surface generation. While the ejecta surface area was determined from the measured size distribution and a geometric configuration governed by a single linear dimension, a complete analytical representation of the comminution and ejection process will require considerable further study and experimentation.

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RésuméFragmentation des rocs mous et durs On rapporte des expériences faites pour étudier la fragmentation de rocs mous et durs, en particulier: du schiste vert et du diorite, soumis aux chocs produits par des boules d'acier de 6,35 mm de diamètre ou par des balles. Les spécimens de rocs au laboratoire étaient des disques de 140 mm de diamètre et d'épaisseurs diverses. La vitesse d'impact des boules lancées d'un canon à gaz comprimé était comprise entre 50 et 260 m/s, tandis que celle des balles tirées d'un canon à poudre était comprise entre 340 et 2500 m/s. On a aussi fait des expériences à l'extérieur en lançant des projectiles d'artillerie de 20 et 40 mm de diamètre contre un mur vertical de schiste vert dans une carrière; la vitesse d'impact était comprise entre 610 et 880 m/s.On a déterminé la taille et la distribution des fragments détachés des diverses cibles, et dans certains cas par une technique photographique la vitesse des fragments. On a mesuré la taille des cratères et des trous produits par les projectiles et, dans certains cas, la déformation plastique du schiste vert a été notée. En plus, dans quelques expériences initiales, l'énergie transférée à un pendule balistique a été determinée. Un effort majeur a été consacré à la mesure de l'énergie des ondes produites par le choc dans les disques de diorite en utilisant une éprouvette sectionnée, munie de jauges de contrainte électrique, et recollée. La conformation des fissures le long d'une coupe diamètrale a été coloriée pour la rendre visible et pour la photographier.Sur un domaine de six décades d'énergie initiale, la profondeur de pénétration dans le schiste correspond d'une manière assez satisfaisante à l'impulsion et à l'énergie initiale; donc le phénomène peut être représenté dans ce domaine par une cible visqueuse. L'énergie de fragmentation, égale à la différence entre l'énergie initiale et la somme de trois termes: l'énergie des ondes dans la cible, l'énergie cinétique des fragments et celle du projectile sortant, est de l'ordre de 70 a 85 pourcent.On n'a pu que déterminer des limites supérieures et inférieures de l'énergie requise pour former les surfaces des fissures à cause de la difficulté de déterminer l'aire de ces surfaces. La surfaces des fragments a été établie, d'après l'hypothèse que la distribution de leurs tailles et leurs configurations géométriques pouvaient être déterminées par une seule mesure de longeur. Cependant, pour arriver à une théorie complète concernant la perte d'énergie et le processus de fragmentation, il faudra une étude et des expériences beaucoup plus étendues.

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With 15 Figures     

Tectonics and oil and gas potentials of the Kolyma and Primor'ye lowlands and adjacent shelves

The impact of gigantic meteorites momentarily creates extremely high pressures and temperatures, leading to the formation of distinctive objects — impact breccias and impactites — at the points where they fall. The Zhamanshin crater is one such place. This annular structure has a diameter of about 10 km, contoured by a low rim made up of a body of shattered Paleozoic rocks thrown out from the ring's center, from depths exceeding 100 - 200 m. Among these breccias have been found pieces and lenticular bodies of remelted rocks — impactites, called zhamanshinites. These thermally altered rocks from a series ranging from baked clays to cinder-like, partly recrystallized substances, glass, and black drops and spattered droplets (up to 1 - 5 cm) of isotropic glass that undoubtedly hardened as they fell through the air. The refused neogenic substances formed by selective evaporation are characterized by a considerable deficit of K and Na, excess Al₂O₃ and SiO₂, a lack of H₂O, and a sharp predominance of Fe⁺² over Fe⁺³. Their characteristic shape and distinctive structure and composition suggests that these remelted droplets are tektites, which were called irgizites when first found in the USSR. Their occurrence in the meteorite crater confirms the idea of a genetic unity between tektites and impactites. Selective evaporation of the more volatile elements is characteristic of the surfaces of small planets lacking an atmosphere, but is not characteristic of the earth's surface. The processes and substances occurring at the impact points of gigantic meteorites are therefore unique on the earth, but highly typical of the surfaces of the Moon, Mars, Mercury, and other relatively small celestial bodies.     

Crystal chemistry and thin film epitaxy of sulfides and Bi-Sb-sulfosalts and their geological application

Summary Metal substitution studies of the stability, structure and chemical bonding of sulfides and sulfosalts lead to significant results, which can be applied to natural parageneses and crystal chemical systematics. Comparison of experiments on stable and metastable phases with thin films provides data, which exceed known geometrical criteria of the sulfosalt systematics. Synthetic and natural phases have been studied with respect to their substitution, bonding chemistry and temperature dependent metal distribution as well as to the structure and orientation of thin films.

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Zusammenfassung Die Untersuchung der Stabilität, Struktur und chemischen Bindung von Sulfosalzen führt zu aussagekräftigen auf natürliche Paragenesen sowie auf die Systematik dieser Verbindungen anwendbaren Resultaten, wenn systematische Substitutionsexperimente angesetzt werden. Diese liefern im Vergleich von stabilen und metastabilen Phasen sowie durch Vergleich mit dünnen Schichten Ergebnisse, die wesentlich über bekannte strukturgeometrische Ansätze zur Sulfosalzsystematik hinausgehen. Es werden synthetische und natürliche Verbindungen bezüglich ihrer Substitution, Bindungschemie und temperaturabhängigen Metallordnung sowie die Orientierung und Struktur von dünnen Schichten diskutiert.

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With 13 Figures

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In memoriam Prof. Dr. V. Kupcik ( 1990)     

Pt-Re-Os and Sm-Nd isotope and HSE and REE systematics of the 2.7 Ga Belingwe and Abitibi komatiites

High-precision Pt-Re-Os and Sm-Nd isotope and highly siderophile element (HSE) and rare earth element (REE) abundance data are reported for two 2.7 b.y. old komatiite lava flows, Tony’s flow (TN) from the Belingwe greenstone belt, Zimbabwe, and the PH-II flow (PH) from Munro Township in the Abitibi greenstone belt, Canada. The emplaced lavas are calculated to have contained ∼25% (TN) and ∼28% (PH) MgO. These lavas were derived from mantle sources characterized by strong depletions in highly incompatible lithophile trace elements, such as light REE (Ce/Sm_N = 0.64 ± 0.02 (TN) and 0.52 ± 0.01 (PH), ε¹⁴³Nd(T) = +2.9 ± 0.2 in both sources). ¹⁹⁰Pt-¹⁸⁶Os and ¹⁸⁷Re-¹⁸⁷Os isochrons generated for each flow yield ages consistent with respective emplacement ages obtained using other chronometers. The calculated precise initial ¹⁸⁶Os/¹⁸⁸Os = 0.1198318 ± 3 (TN) and 0.1198316 ± 5 (PH) and ¹⁸⁷Os/¹⁸⁸Os = 0.10875 ± 17 (TN) and 0.10873 ± 15 (PH) require time-integrated ¹⁹⁰Pt/¹⁸⁸Os and ¹⁸⁷Re/¹⁸⁸Os of 0.00178 ± 11 and 0.407 ± 8 (TN) and 0.00174 ± 18 and 0.415 ± 5 (PH). These parameters, which by far represent the most precise and accurate estimates of time-integrated Pt/Os and Re/Os of the Archean mantle, are best matched by those of enstatite chondrites. The data also provide evidence for a remarkable similarity in the composition of the sources of these komatiites with respect to both REE and HSE. The calculated absolute HSE abundances in the TN and PH komatiite sources are within or slightly below the range of estimates for the terrestrial Primitive Upper Mantle (PUM). Assuming a chondritic composition of the bulk silicate Earth, the strong depletions in LREE, yet chondritic Re/Os in the komatiite sources are apparently problematic because early Earth processes capable of fractionating the LREE might also be expected to fractionate Re/Os. This apparent discrepancy could be reconciled via a two-stage model, whereby the moderate LREE depletion in the sources of the komatiites initially occurred within the first 100 Ma of Earth’s history as a result of either global magma ocean differentiation or extraction and subsequent long-term isolation of early crust, whereas HSE were largely added subsequently via late accretion. The komatiite formation, preceded by derivation of basaltic magmas, was a result of second-stage, large-degree dynamic melting in mantle plumes.     

Fact and fiction: Geography and literature

Main epistemological reflections in Geography developed since the 1970s emphasize holistic perspectives in which intuition has an important cognitive. Bringing forward the ideas lifeworld and espace véçu important currents in this approach put in relief the sense of place, the affective ties with the environment, the aesthetic and landscape symbology, the genius loci and the spatial-temporal rythms connected to personal experiences. In this context, literary works (tales, novels, or short stories) are important because they provide authentic and indespensable testimony of the influence of human experience on place.The analysis of the vast bibliography on geographic interpretation of literary sources reveals typologies: studies on the links between real and literary landscapes, understanding of the sense of place, the concepts of rooting and uprooting, the definitions of inscapes and territorial consciousness. These five thematic foci allow the interpretation of the relationship existing between geography — regarded as landscape and place — and literary works —considered as the expression to define and fix the culture and feelings of a human group with respect to its own space and place.     

Chemical and Isotopic Characteristics of the Water and Suspended Particulate Materials in the Yangtze River and Their Geological and Environmental Implications

The chemical and isotopic characteristics of the water and suspended particulate materials（SPM） in the Yangtze River were investigated on the samples collected from 25 hydrological monitoring stations in the mainsteam and 13 hydrological monitoring stations in the major tributaries during 2003 to 2007. The water samples show a large variation in both δD（ 30‰ to 112‰） and δ18O（ 3.8‰ to 15.4‰） values. Both δD and δ18O values show a decrease from the river head to the Jinsha Jiang section and then increase downstream to the river mouth. It is found that the oxygen and hydrogen isotopic compositions of the Yangtze water are controlled by meteoric precipitation, evaporation, ice（and snow） melting and dam building. The Yangtze SPM concentrations show a large variation and are well corresponded to the spatial and temporal changes of flow speed, runoff and SPM supply, which are affected by the slope of the river bed, local precipitation rate, weathering intensity, erosion condition and anthropogenic activity. The Yangtze SPM consists of clay minerals, clastic silicate and carbonate minerals, heavy minerals, iron hydroxide and organic compounds. From the upper to lower reaches, the clay and clastic silicate components in SPM increase gradually, but the carbonate components decrease gradually, which may reflect changes of climate and weathering intensity in the drainage area. Compared to those of the upper crust rocks, the Yangtze SPM has lower contents of SiO2, CaO, K2 O and Na2 O and higher contents of TFe2 O3 and trace metals of Co, Ni, Cu, Zn, Pb and Cd. The ΣREE in the Yangtze SPM is also slightly higher than that of the upper crust. From the upper to lower reaches, the CaO and MgO contents in SPM decrease gradually, but the SiO2 content increases gradually, corresponding to the increase of clay minerals and decrease of the carbonates. The δ30SiSPM values（ 1.1‰ to 0.3‰） of the Yangtze SPM are similar to those of the average shale, but lower than those of the granite rocks（ 0.3‰ to 0.3‰）, reflecting the effect of silicon isotope fractionation in silicate weathering process. The δ30SiSPM values of the Yangtze SPM show a decreasing trend from the upper to the middle and lower reaches, responding to the variation of the clay content. The major anions of the river water are HCO 3, SO 4 2, Cl, NO 3, SiO 4 4 and F and the major cations include Ca2＋, Na＋, Mg2＋, K＋ and Sr2＋. The good correlation between HCO3-content and the content of Ca2＋may suggest that carbonate dissolution is the dominate contributor to the total dissolved solid（TDS） of the Yangtze River. Very good correlations are also found among contents of Cl, SO4 2, Na＋, Mg2＋, K＋and Sr2＋, indicating the important contribution of evaporite dissolution to the TDS of the Yangtze River. High TDS contents are generally found in the head water, reflecting a strong effect of evaporation in the Qinghai-Tibet Plateau. A small increase of the TDS is generally observed in the river mouth, indicating the influence of tidal intrusion. The F and NO3 contents show a clear increase trend from the upstream to downstream, reflecting the contribution of pesticides and fertilizers in the Chuan Jiang section and the middle and lower reaches. The DSi shows a decrease trend from the upstream to downstream, reflecting the effect of rice and grass growth along the Chuan Jiang section and the middle and lower reaches. The dissolved Cu, Zn and Cd in the Yangtze water are all higher than those in world large rivers, reflecting the effect of intensive mining activity along the Yangtze drainage area. The Yangtze water generally shows similar REE distribution pattern to the global shale. The δ30SiDiss values of the dissolved silicon vary from 0.5‰ to 3.7‰, which is the highest among those of the rivers studied. The δ30SiDiss values of the water in the Yangtze mainsteam show an increase trend from the upper stream to downstream. Its DSi and δ30SiDiss are influenced by multiple processes, such as weathering process, phytolith growth in plants, evaporation, phytolith dissolution, growth of fresh water diatom, adsorption and desorption of aqueous monosilicic acid on iron oxide, precipitation of silcretes and formation of clays coatings in aquifers, and human activity. The δ34SSO4 values of the Yangtze water range from 1.7‰ to 9.0‰. The SO4 in the Yangtze water are mainly from the SO4 in meteoric water, the dissolved sulfate from evaporite, and oxidation of sulfide in rocks, coal and ore deposits. The sulfate reduction and precipitation process can also affect the sulfur isotope composition of the Yangtze water. The87Sr/86Sr ratios of the Yangtze water range from 0.70823 to 0.71590, with an average value of 0.71084. The87Sr/86Sr ratio and Sr concentration are primary controlled by mixing of various sources with different87Sr/86Sr ratios and Sr contents, including the limestone, evaporite and the silicate rocks. The atmospheric precipitation and anthropogenic inputs can also contribute some Sr to the river. The δ11B values of the dissolved B in the Yangtze water range from 2.0‰ to 18.3‰, which is affected by multifactors, such as silicate weathering, carbonate weathering, evaporite dissolution, atmospheric deposition, and anthropogenic inputs.     

Numerical simulations and parametric study of SDCM and DCM piles under full scale axial and lateral loads

The new kind of reinforced Deep Cement Mixing (DCM) pile namely, Stiffened Deep Cement Mixing (SDCM) pile is introduced to mitigate the problems due to the low flexural resistance, quality control problem and unexpected failure of DCM pile. The SDCM pile consists of DCM pile reinforced with concrete core pile. Previously, the full scale pile load test and the full scale embankment loading test were successfully conducted in the field. To continue the study on the behavior of SDCM and DCM piles, the 3D finite element simulations using PLAXIS 3D Foundation Software were conducted in this study. The simulations of full scale pile load test consisted of two categories of testing which are the axial compression and the lateral loading. For DCM C-1 and C-2 piles, the clay–cement cohesion, C_DCM, and clay–cement modulus, E_DCM, were obtained from simulations as 300 kPa and 200 kPa as well as 60,000 kPa and 40,000 kPa, respectively. For the SDCM piles, the simulation results show that increasing length ratio, L_core/L_DCM, increased the bearing capacity whereas the sectional area ratio, A_core/A_DCM, has only small effects on the bearing capacity for the axial compression loading. The verified parameters such as the clay–cement cohesion, C_DCM, and clay–cement modulus, E_DCM, from simulations of axial compression tests were 200 kPa and 30,000 kPa, respectively. On the other hand, increasing the sectional area ratio, A_core/A_DCM, significantly influenced the ultimate lateral resistance while the length ratio, L_core/L_DCM, is not significant in the ultimate lateral load capacity when the length of concrete core pile is longer than 3.5 m. In addition, the tensile strength of DCM, T_DCM, and concrete core pile, T_core, are very important to the lateral pile resistance. The back-calculation results from simulations of tensile strength were 5000 kPa and 50 kPa for the T_core and T_DCM, respectively.     

Cu- and Mn-bearing tourmalines from Brazil and Mozambique: crystal structures, chemistry and correlations

Cu- and Mn-bearing tourmalines from Brazil and Mozambique were characterised chemically (EMPA and LA-ICP-MS) and by X-ray single-crystal structure refinement. All these samples are rich in Al, Li and F (fluor-elbaite) and contain significant amounts of CuO (up to ~1.8 wt%) and MnO (up to ~3.5 wt%). Structurally investigated samples show a pronounced positive correlation between the <Y-O> distances and the (Li + Mn²⁺ + Cu + Fe²⁺) content (apfu) at this site with R ² = 0.90. An excellent negative correlation exists between the <Y-O> distances and the Al₂O₃ content (R ² = 0.94). The samples at each locality generally show a strong negative correlation between the X-site vacancies and the (MnO + FeO) content. The Mn content in these tourmalines depends on the availability of Mn, on the formation temperature, as well as on stereochemical constraints. Because of a very weak correlation between MnO and CuO we believe that the Cu content in tourmaline is essentially dependent on the availability of Cu and on stereochemical constraints.     

Diffusion and solubility of hydrogen and water in periclase

Cylinders of synthetic periclase single crystals were annealed at 0.15–0.5 GPa and 900–1200 °C under water-saturated conditions for 45 min to 72 h. Infrared spectra measured on the quenched products show bands at 3,297 and 3,312 cm^?1 indicating V _OH ^? centers (OH-defect stretching vibrations in a half-compensated cation vacancy) in the MgO structure as a result of proton diffusion into the crystal. For completely equilibrated specimens, the OH-defect concentration, expressed as H₂O equivalent, was calculated to 3.5 wt ppm H₂O at 1,200 °C and 0.5 GPa based on the calibration method of Libowitzky and Rossmann (Am Min 82:1111–1115, 1997). This value was confirmed via Raman spectroscopy, which shows OH-defect-related bands at identical wavenumbers and yields an H₂O equivalent concentration of about 9 wt ppm using the quantification scheme of Thomas et al. (Am Min 93:1550–1557, 2008), revised by Mrosko et al. (Am Mineral 96:1748–1759, 2011). Results of both independent methods give an overall OH-defect concentration range of 3.5–9 (+4.5/?2.6) ppm H₂O. Proton diffusion follows an Arrhenius law with an activation energy E _a = 280 ± 64 kJ mol^?1 and the logarithm of the pre-exponential factor logD_o (m² s^?1) = ?2.4 ± 1.9. IR spectra taken close to the rims of MgO crystals that were exposed to water-saturated conditions at 1,200 °C and 0.5 GPa for 24 h show an additional band at 3,697 cm^?1, which is related to brucite precipitates. This may be explained by diffusion of molecular water into the periclase, and its reaction with the host crystal during quenching. Diffusion of molecular water may be described by logD_H2O (m² s^?1) = ?14.1 ± 0.4 (2σ) at 1,200 °C and 0.5 GPa, which is ~ 2 orders of magnitude slower than proton diffusion at identical P-T conditions.     

Kinetic and equilibrium mass-dependent isotope fractionation laws in nature and their geochemical and cosmochemical significance

The mass-dependent fractionation laws that describe the partitioning of isotopes are different for kinetic and equilibrium reactions. These laws are characterized by the exponent relating the fractionation factors for two isotope ratios such that α_2/1 = α_3/1^β. The exponent β for equilibrium exchange is (1/m₁ − 1/m₂)/(1/m₁ − 1/m₃), where m_i are the atomic masses and m₁ < m₂ < m₃. For kinetic fractionation, the masses used to evaluate β depend upon the isotopic species in motion. Reduced masses apply for breaking bonds whereas molecular or atomic masses apply for transport processes. In each case the functional form of the kinetic β is ln(M₁/M₂)/ln(M₁/M₃), where M_i are the reduced, molecular, or atomic masses. New high-precision Mg isotope ratio data confirm that the distinct equilibrium and kinetic fractionation laws can be resolved for changes in isotope ratios of only 3‰ per amu. The variability in mass-dependent fractionation laws is sufficient to explain the negative Δ¹⁷O of tropospheric O₂ relative to rocks and differences in Δ¹⁷O between carbonate, hydroxyl, and anhydrous silicate in Martian meteorites. (For simplicity, we use integer amu values for masses when evaluating β throughout this paper.)     

Fractionation of carbon and oxygen isotopes and magnesium between coexisting metamorphic calcite and dolomite

Fractionations of carbon and oxygen isotopes and magnesium between coexisting dolomite and calcite have been determined for marbles and calcareous schists of a wide variety of metamorphic environments from Vermont and the Grenville Province of Ontario. Concordant equilibrium fractionations are given by 83% of the samples. Calibration of the isotopic thermometers using the Mg-calcite solvus thermometer gave in the temperature range: 650°>T°>100°C $$ \begin{gathered} 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.45 (10^6 T^{ - 2} ) - 0.40 \hfill \\ 1,000\ln \alpha _{D - Ct}^{O^{18} } = 0.18 (10^6 T^{ - 2} ) + 0.17. \hfill \\ \end{gathered} $$ These isotopic fractionation expressions differ significantly from the experimentally derived relations, including the dolomite-Mg-calcite C¹³ partial exchange experiments of this study. Temperature ranges obtained for the metamorphic zones of Vermont are: chlorite zone, 210° to 295° C; biotite zone, 255° to 400° C; staurolite-kyanite zone, 110° to 550° C. In amphibolite-facies rocks the quenched partition relations can be complex. The temperature of quench or recrystallization may be as large as 400° C below the inferred metamorphic maximum. Oxygen isotope disequilibrium in high grade rocks, particularly from the Chester dome area, Vermont, is characterized by large negative δO _D ¹⁸ –δO _Ct ¹⁸ values. The size of the equilibrium exchange system for carbon and oxygen isotopes and magnesium is small, less than a few inches across the inferred relict bedding. This is attributed to the lack of a mobile pore fluid except in systems undergoing decarbonation. C¹³/C¹² ratios in Grenville and Vermont marbles and O¹⁸/O¹⁶ ratios in Grenville and greenschist-facies Vermont carbonates span the range of ancient limestones. Staurolite-kyanite zone calcareous schists and marbles from the Chester dome area, Vermont are depleted in O¹⁸(δO¹⁸=12 to 20‰) due to equilibrium or disequilibrium decarbonation and some partial exchange. Extrapolation of the dolomite-calcite fractionation expressions to 20° C indicates that dolomite is enriched in O¹⁸ by about 4.9‰ and in C¹³ by about 2.4‰.     

Divariant and trivariant reaction line slopes in FMAS and CFMAS: theory and applications

The theory of divariant reactions is investigated in some detail and approaches involving simultaneously operating reactions and X _Mg isopleths are combined. Using the Gibbs' method (Spear et al. 1982), a general equation is derived for X _Mg isopleth slopes in FMAS and CFMAS, which may be applied to any divariant assemblage in these systems. Isopleth slopes are calculated for a number of divariant FMAS and CFMAS reactions inferred to have operated in Sri Lankan granulites, giving more rigorous constraints on the local P-T path. Isopleth slopes are also calculated for the trivariant CFMAS reaction orthopyroxene + plagioclase = garnet + quartz. The resulting dP/dT range from +8 to +18 bar/K. Application to Sri Lankan granulites confirms an earlier hypothesis (Faulhaber and Raith 1991) that a retrograde path with a dP/dT of ～10–15 bar/K may cause garnet growth in charnockites and garnet breakdown in metabasites. It is shown here that dP/dT depends primarily on the Ca contents of garnet and plagioclase. Large variations in isopleth and reaction line slopes are possible, due to the thermodynamic effect of additional components in solid solutions, e.g. albite in plagioclase. This has a good potential for the assessment of the exact form of P-T paths. Equations to calculate isopleth slopes could be included in software packages aimed at defining P-T estimates, enabling geologists to derive realistic P-T paths.     

Source and distribution of trace metals and nutrients in Narmada and Tapti river basins,India

The study was designed to establish the distributions of trace metals, dissolved organic carbon, and inorganic nutrients as well as to assess the extent of anthropogenic inputs into the Narmada and Tapti rivers. Water and sediment qualities are variable in the rivers, and there are major pollution problems at certain locations, mainly associated with urban and industrial centers. The metal concentrations of samples of the aquatic compartments investigated were close to the maximum permissible concentration for the survival of aquatic life, except for higher values of Cu (5–763 μg l⁻¹), Pb (24–376 μg l⁻¹), Zn (24–730 μg l⁻¹), and Cr (70–740 μg l⁻¹) and for drinking water except for elevated concentrations of metals such as Pb, Fe (850–2,060 μg l⁻¹), Cr, and Ni (20–120 μg l⁻¹). In general, the concentrations of trace metals in the rivers vary down stream which may affect the “health” of the aquatic ecosystem and may also affect the health of the rural community that depends on the untreated river water directly for domestic use. The assessment of EF, I _geo, and PLI in the sediments reveals overall moderate pollution in the river basins.     

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.     

Breakdown of hydrous ringwoodite to pyroxene and spinelloid at high P and T and oxidizing conditions

To get deeper insight into the phase relations in the end-member system Fe₂SiO₄ and in the system (Fe, Mg)₂SiO₄ experiments were performed in a multi-anvil apparatus at 7 and 13 GPa and 1,000–1,200°C as a function of oxygen fugacity. The oxygen fugacity was varied using the solid oxygen buffer systems Fe/FeO, quartz–fayalite–magnetite, MtW and Ni/NiO. The run products were characterized by electron microprobe, Raman- and FTIR-spectroscopy, X-ray powder diffraction and transmission electron microscopy. At fO₂ corresponding to Ni/NiO Fe-ringwoodite transforms to ferrosilite and spinelloid according to the reaction: 9 Fe₂SiO₄ + O₂ = 6 FeSiO₃ + 5 Fe_2.40Si_0.60O₄. Refinement of site occupancies in combination with stoichiometric Fe³⁺ calculations show that 32% of the total Fe is incorporated as Fe³⁺ according to From the Rietveld refinement we identified spl as spinelloid III (isostructural with wadsleyite) and/or spinelloid V. As we used water in excess in the experiments the run products were also analyzed for structural water incorporation. Adding Mg to the system increases the stability field of ringwoodite to higher oxygen fugacity and the spinel structure seems to accept higher Fe³⁺ but also water concentrations that may be linked. At oxygen fugacity corresponding to MtW conditions similar phase relations in respect to the breakdown reaction in the Fe-end-member system were observed but with a strong fractionation of Fe into spl and Mg into coexisting cpx. Thus, through this strong fractionation it is possible to stabilize very Fe-rich wadsleyite with considerable Fe³⁺ concentrations even at an intermediate Fe–Mg bulk composition: assuming constant K _D independent on composition and a bulk composition of x _Fe = 0.44 this fractionation would stabilize spl with x _Fe = 0.72. Thus, spl could be a potential Fe³⁺ bearing phase at P–T conditions of the transition zone but because of the oxidizing conditions and the Fe-rich bulk composition needed one would expect it more in subduction zone environments than in the transition zone in senso stricto.

A-type granites and related rocks: Petrogenesis and classification

The problems of identification of A-type granitoids are analyzed. These rocks occur in different geodynamic settings. Owing to their mantle nature, they show distinct REE specialization. These are acid intrusive rocks, whose volcanic products are of crucial scientific and practical significance. However, neither the great number of proposed classification schemes and diagrams, including those based on expensive analytical data, nor hot scientific discussions of their identification and the ambiguity of the term A-granitoids helped to determine their classification features in full measure. A principally new discriminant diagram is proposed for the classification of igneous A-type rocks, based on the analysis of earlier obtained results and the petrochemical composition of these rocks. A comparative analysis of subdivision of granites and related felsic volcanic rocks (SiO₂ > 67 wt.%), based on the ternary (Na₂O + K₂O)–Fe₂O₃* x 5–(CaO + MgO) x 5 and other widely applied diagrams, has shown the advantage of the proposed discriminant diagram for the classification of A-type granitoids from different geodynamic settings.