Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.     

Hydrogeology of the Kabul Basin (Afghanistan), part I: aquifers and hydrology

Shallow groundwater represents the main source for water supply in Kabul, Afghanistan. Detailed information on the hydrogeology of the Kabul Basin is therefore needed to improve the current supply situation and to develop a sustainable framework for future groundwater use. The basin is situated at the intersection of three major fault systems of partially translational and extensional character. It comprises three interconnected aquifers, 20–70 m thick, consisting of coarse sandy to gravely detritus originating from the surrounding mountains. The aquifers were deposited by three rivers flowing through the basin. The coarse aquifer material implies a high permeability. Deeper parts are affected by cementation of pore spaces, resulting in formation of semi-diagenetic conglomerates, causing decreased well yields. Usually the aquifers are covered by low-permeability loess which acts as an important protection layer. The main groundwater recharge occurs after the snowmelt from direct infiltration from the rivers. The steadily rising population is estimated to consume 30–40 million m³ groundwater per year which is contrasted by an estimated recharge of 20–45 million m³/a in wet years. The 2000–2005 drought has prevented significant recharge resulting in intense overexploitation indicated by falling groundwater levels.     

The freshwater lens of Benjamín Aceval,Chaco, Paraguay: a terrestrial analogue of an oceanic island lens

The occurrence of a freshwater lens in the Paraguayan Chaco, 900 km away from the ocean, is reported. It is located underneath sandstone hills, surrounded by lowlands with predominantly saline groundwater. Its geometry was delineated using geoelectrical and electromagnetic investigations. The unusual height of the fresh groundwater level can be attributed to the presence of a confining layer at depth. The lens receives its recharge exclusively from rainfall during the hot and humid summer months. It predominantly contains water predating the atmospheric atomic bomb tests, some of it probably up to a thousand or more years old. The water balance shows that extraction currently does not exceed recharge in normal years. However, the available volume of groundwater leaves little room for a further increase of extraction in the future. Recharge is augmented by return flow from thousands of latrines and cess pits, and this has lead to widespread contamination of the groundwater by faecal bacteria.     

Monitoring of atmospheric deposition in European forests and an overview on its implication on forest condition

Forest conditions in Europe have been monitored over 20 years jointly by the International Cooperative Programme on Assessment and Monitoring of Air Pollution Effects on Forests (ICP Forests) and the European Union (EU). Maps for mean bulk SO₄, NO₃ and NH₄ deposition at around 400 intensive monitoring plots in the years 1999–2001, as well as time trends for the period 1996–2001, are presented. Mean bulk SO₄ deposition at 169 plots mostly located in central Europe decreased from 7.4 to 5.8 kgS ha⁻¹ a⁻¹. Mean NH₄ bulk deposition decreased from 6.2 to 5.3 kgN ha⁻¹ a⁻¹. Nitrate bulk deposition fluctuated around 5 kgN ha⁻¹ a⁻¹. On average, throughfall deposition was considerably higher than bulk deposition. Time trends for mean tree crown defoliation as an overall indicator for forest condition show a peak in the mid 1990s for most of the monitored main tree species and a recent increase for the years 2003 and 2004. Multivariate linear regression analyses show some significant relations between deposition and defoliation. These relations depend on the tree species and site characteristics. Effects of deposition are moderated by the influence of biotic stress factors such as insects and fungi and by abiotic stress factors, such as weather.     

Sr-gorceixite,a weathering product in rich iron ores from the Córrego do Feijão Mine,Minas Gerais,Brazil

A sulfate-bearing Sr-Ba phosphate (Sr-gorceixite) formed by supergene alteration in rich iron ores from Minas Gerais, Brazil, has been studied by means of microprobe techniques. Analytical data and the structural formula are presented.     

Polymetamorphose und Deckenbau der Strand-Halbinsel/SW-Norwegen

Zusammenfassung Die Metamorphite der Halbinsel Strand / SW-Norwegen gehören zu einem Deckensystem präkambrischer Gesteine, das während der kaledonischen Orogenese von NNW her auf den Baltischen Schild geschoben worden ist (Sigmond Kildal 1978). Eine hangende Deckeneinheit umfa\t Metagranite, Melagabbroide und Gneise. Ihr granulitfazieller Mineralbestand (Metamorphosealter 1,5 Milliarden Jahre) wurde wahrscheinlich vor 1,18 Milliarden Jahren grünschieferfaziell retrograd überprägt. Die Decke ist nur noch in kleinen Erosionsinseln vorhanden. Eine liegende Dekkeneinheit besteht aus metasedimentären Gesteinen. Sie weist Mineralbestände der höheren Amphibolitfazies auf, die ebenfalls grünschieferfaziell überprägt wurden. Die Al^VI-Gehalte der bei beiden metamorphen Prozessen gebildeten Amphibole deuten bei Anwendung eines Diagramms vonRaase (1974) an, da\ die retrograde Metamorphose hier bei höheren Drücken ablief als die ältere Metamorphose. Ein Gesamtgesteinsalter von 1,16 Milliarden Jahren scheint für diese grünschieferfazielle Metamorphose das gleiche orogene Ereignis anzuzeigen wie für die hangende Einheit. Produkt der schwachen kaledonischen Metamorphose (400 Millionen Jahre) ist Stilpnomelan, der auch im Grundgebirge des Baltischen Schildes auftritt.

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The Strand Peninsula, Stavanger district, Southwestern Norway, has become well known, when V. M.Goldschmidt (1920) published his hypothesis of regional metasomatism. All rocks of the Strand area were assumed to be situated in autochthonous position. The main point ofGoldschmidt's hypothesis was progarde metamorphism of argillaceous sediments and their transformation to albite schists and plagioclase gneisses by metasomatic solutions given off from intruded trondhjemitic magmas.However, in contrast toGoldschmidt's ideas, the granitoid sill of the Ormakam-Moldhesten area, Strand Peninsula, and its wall rocks, which played an important role inGoldschmidt's discussion, are now found to be parts of a polymetamorphous thrust unit.Granulite facies assemblages, mainly consisting of orthopyroxene +clinopyroxene+plagioclase+hastingsite±orthoclase and quartz, have been partially replaced by lowgrade assemblages. Probably, the high-grade metamorphism has an age of about 1.5 Ga (Andresen &Heier 1975) whereas the age of the greenschist facies event may be conform to an orogenic cycle at about 1.15 Ga (Sigmond Kildal 1978).A lower nappe, covering the Strand Peninsula for its most parts, was subject of a petrologic re-examination using the microscope and the microprobe analyser. Its contacts with the hanging nappe as well as those with the underlying gneissic basement are characterized by thrust planes and horizons of phyllonites and cataclasites inside of the nappe and by local brecciation in the uppermost zones of the basement.The rocks of the lower nappe have been formed a long with the upper amphibolite facies as indicated by the following mineral assemblage: andesine + hastingsite and Mg-hornblende + quartz +biotite.Obviously, an inverse order of temperature regimes is recognizable in the allochthonous units. Maximum temperature of the upper nappe reached 800C (Müller &Herbert 1984) whereas T_max of the lower nappe did not exceed 750C.Using a diagram ofRaase (1974) the Al^VI-contents of the primary hastingsitic hornblendes of the lower nappe rocks indicate pressures which range distinctly below 5 kbars, whereas the secondary pargasitic hornblendes were formed at pressures of about 5 kbars. Probably the thrusting happened before the formation of secondary hornblendes took place. The load pressure in the lower nappe (< 5 kbars) was distinctly increased when the upper nappe was thrusted upon the lower one. Consequently the Al^VI-contents of secondary hornblendes indicate increased pressure ( 5 kbars).In the gneisses of the lower nappe late fractures were filled by stilpnomelane, chlorite and quartz. Very probably this depends on thrust movements during the Caledonian orogeny.Verschure et al. (1980) found a similar stilpnomelane formation in adjacent terrains of the basement and proposed a weak Caledonian metamorphism of about 400 my.

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Résumé Les roches métamorphiques de la presqu'Île de Strand (sud-ouest de la Norvège) appartiennent à un empilement de nappes formées de roches pré-cambriennes et charriées vers le SSE sur le bouclier baltique au cours de l'orogenèse calédonienne (Sigmond Kildal 1978).Une nappe supérieure comprend des métagranites, des mélagabbroÏdes et des gneiss. Leurs paragenèses, du facies des granulites (âge du métamorphisme: 1,5 Ga) ont été rétromorphosées dans le facies des schistes verts il y a probablement 1,18 Ga. Cette nappe ne subsiste qu'en petits fragments épargnés par l'érosion.Une nappe inférieure est composée de roches métasédimentaires. Ces roches présentent des paragenèses du faciès supérieur des amphibolites, également rétromorphosées dans le facies des schistes verts. L'application du diagramme de Raase (1974) aux teneurs en Al^VI des amphiboles formées lors des deux processus métamorphiques indique que la rétromorphose s'est déroulée à une pression supérieure à celle du métamorphisme ancien. Un âge de 1,16 Ga sur roche totale semble indiquer que le mÊme processus orogénique a servi de cadre à la rétromorphose en facies des schistes verts dans les deux nappes.Du stilpnomélane, présent tant dans la nappe inférieure que dans le bouclier baltique autochtone, témoigne d'un métamorphisme calédonien (400 Ma) de faible degré.

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Strand ( ) , NNW (Sigmond KILDAL, 1978). , . - 1,5 , 118 , . . . , . Al^VI , , RAASE (1974) , , . 1,6 , , , . (400 ) , .

     

Site occupation and electric field gradient in acentric neptunite-measurements and evaluations concerning powder- and single crystal – Mössbauer spectroscopy and x-ray diffractometry

Mössbauer measurements on neptunite (KNa₂Li(Fe,Mn,Mg)₂Ti₂Si₈O₂₄) at 400?K reveal the distribution of Fe-ions on the crystallographic sites in agreement with neutron diffraction results published elsewhere. Even the previously postulated small amount of Fe-ions on the Ti(2) site has been detected, combined with a charge transfer which is in agreement with optical absorption investigations by other authors. A qualitative site occupation model is able to explain the different features of our observations. Single crystal Mössbauer measurements with the k-vector of incident γ-rays parallel to the crystallographic b-axis (space group Cc) of neptunite at different temperatures yield the angle β between the main component of the electric field gradient (EFG), V _zz and b. This angle is in close accordance with a calculated value of β for the Fe(1) position from electron density maps. The latter also reveal an absolute value of V _zz which is in satisfactory agreement with V _zz derived from Mössbauer spectroscopy.     

Inverse modeling and uncertainty analysis of potential groundwater recharge to the confined semi-fossil Ohangwena II Aquifer,Namibia

The identification of potential recharge areas and estimation of recharge rates to the confined semi-fossil Ohangwena II Aquifer (KOH-2) is crucial for its future sustainable use. The KOH-2 is located within the endorheic transboundary Cuvelai-Etosha-Basin (CEB), shared by Angola and Namibia. The main objective was the development of a strategy to tackle the problem of data scarcity, which is a well-known problem in semi-arid regions. In a first step, conceptual geological cross sections were created to illustrate the possible geological setting of the system. Furthermore, groundwater travel times were estimated by simple hydraulic calculations. A two-dimensional numerical groundwater model was set up to analyze flow patterns and potential recharge zones. The model was optimized against local observations of hydraulic heads and groundwater age. The sensitivity of the model against different boundary conditions and internal structures was tested. Parameter uncertainty and recharge rates were estimated. Results indicate that groundwater recharge to the KOH-2 mainly occurs from the Angolan Highlands in the northeastern part of the CEB. The sensitivity of the groundwater model to different internal structures is relatively small in comparison to changing boundary conditions in the form of influent or effluent streams. Uncertainty analysis underlined previous results, indicating groundwater recharge originating from the Angolan Highlands. The estimated recharge rates are less than 1% of mean yearly precipitation, which are reasonable for semi-arid regions.     

Discrete element model for crack propagation in brittle materials

We propose a discrete element model for brittle rupture. The material consists of a bidimensional set of closed‐packed particles in contact. We explore the isotropic elastic behavior of this regular structure to derive a rupture criterion compatible to continuum mechanics. We introduce a classical criterion of mixed mode crack propagation based on the value of the stress intensity factors, obtained by the analysis of two adjacent contacts near a crack tip. Hence, the toughness becomes a direct parameter of the model, without any calibration procedure. We verify the consistency of the formulation as well as its convergence by comparison with theoretical solutions of tensile cracks, a pre‐cracked beam, and an inclined crack under biaxial stress. Copyright © 2015 John Wiley & Sons, Ltd.