Volume diffusion of Ytterbium in YAG: thin-film experiments and combined TEM–RBS analysis

In this study, we address volume diffusion of ytterbium in yttrium aluminum garnet (YAG) using thin-film single crystal diffusion couples. We employ analytical transmission electron microscopy (ATEM) as a tool for combined microstructural and microchemical analysis and compare the results to Rutherford backscattering (RBS) analysis. Given the high spatial resolution of the method, we focus on microstructural changes of the thin-film diffusant source during the diffusion anneal. We evaluate the potential influence of the associated changes in its transport properties on the evolution of concentration profiles in the single crystal substrate. This approach allows us to test the reliability of determination of volume diffusion coefficients from thin-film diffusion experiments. We found that for the chosen experimental setting, the influence of thin-film re-crystallization is small when compared with the experimental uncertainty and good estimates for the volume diffusion coefficients of Yb in YAG can be obtained using standard assumptions. Both Yb-concentration profiles analyzed with ATEM and with RBS give similar results. At 1,450°C and 1 bar, we infer log D _Yb (m²/s) values of −19.37 ± 0.07 (TEM) and −19.84 ± 0.02 (RBS). Although the change in thin-film transport properties associated with successive crystallization during the diffusion anneal does not play a major role for our experimental setup, this effect cannot generally be ignored.     

Shoshonite and sub-alkaline magmas from an ultrapotassic volcano: Sr–Nd–Pb isotope data on the Roccamonfina volcanic rocks,Roman Magmatic Province,Southern Italy

The Roccamonfina volcano is characterised by two stages of volcanic activity that are separated by volcano-tectonic caldera collapses. Ultrapotassic leucite-bearing rocks are confined to the pre-caldera stage and display geochemical characteristics similar to those of other volcanoes in the Roman Province. After the major sector collapse of the volcano, occurred at ca. 400 ka, shoshonitic rocks erupted from cinder cones and domes both within the caldera and on the external flanks of the pre-caldera Roccamonfina volcano. On the basis of new trace element and Sr–Nd–Pb isotope data, we show that the Roccamonfina shoshonitic rocks are distinct from shoshonites of the Northern Roman Province, but are very similar to those of the Neapolitan volcanoes. The last phases of volcanic activity erupted sub-alkaline magmas as enclaves in trachytic domes, and as lavas within the Monte Santa Croce dome. Ultrapotassic rocks of the pre-caldera composite volcano are plagioclase-bearing leucitites characterised by high levels of incompatible trace elements with an orogenic signature having troughs at Ba, Ta, Nb, and Ti, and peaks at Cs, K, Th, U, and Pb. Initial values of ⁸⁷Sr/⁸⁶Sr range from 0.70926 to 0.70999, ¹⁴³Nd/¹⁴⁴Nd ranges from 0.51213 to 0.51217, while the lead isotope rations vary between 18.788–18.851 for ²⁰⁶Pb/²⁰⁴Pb, 15.685–15.701 for ²⁰⁷Pb/²⁰⁴Pb, and 39.048–39.076 for ²⁰⁸Pb/²⁰⁴Pb. Shoshonites show a similar pattern of trace element depletions and enrichments to the earlier ultrapotassic leucite-bearing rocks but have a larger degree of differentiation and lower concentrations of incompatible trace elements. On the other hand, shoshonitic rocks have Sr, Nd, and Pb isotopes consistently different than pre-caldera ultrapotassic leucite-bearing rocks. ⁸⁷Sr/⁸⁶Sr ranges from 0.70665 to 0.70745, ¹⁴³Nd/¹⁴⁴Nd ranges from 0.51234 to 0.51238, ²⁰⁶Pb/²⁰⁴Pb ranges from 18.924 to 19.153, ²⁰⁷Pb/²⁰⁴Pb ranges from 15.661 to 15.694, and ²⁰⁸Pb/²⁰⁴Pb ranges from 39.084 to 39.212. High-K calc-alkaline samples have intermediate isotopic values between ultrapotassic plagioclase leucitites and shoshonites, but the lowest levels of incompatible trace element contents. It is argued that ultrapotassic magmas were generated in a modified lithospheric mantle after crustal-derived metasomatism. Interaction between the metasomatic agent and lithospheric upper mantle produced a low-melting point metasomatised veined network. The partial melting of the veins alone produced pre-caldera leucite-bearing ultrapotassic magmas. It was possibly triggered by either post-collisional isotherms relaxation or increasing T°C due increasing heat flow through slab tears. Shoshonitic magmas were generated by further melting, at higher temperature, of the same metasomatic assemblage with addition 10–20% of OIB-like astenospheric mantle material. We suggest that addition of astenospheric upper mantle material from foreland mantle, flowing through slab tearing after collision was achieved. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

On the possibility of forecasting the long-term air temperature variability that determines the hydrophysical structure and ecology of the Black Sea waters

Periods and amplitudes of long-term temperature fluctuations were obtained using the methods of spectral analysis and filtration of secular time series of the air temperature at 13 hydrometeorological stations in the Black Sea region. The prognostic calculations of the long-term air temperature variability are based on the results of processing of time series. The calculations of the air temperature agree with the data of observations. The possibility of the long-term air temperature variability prediction is shown.     

Erosion processes in karst landscapes of the Russian plain northern taiga,based on digital elevation modeling

This paper considers the problems of the potential development of erosion processes in the natural landscapes of northern taiga in the Russian plain. It is considered that in forest ecosystems, erosion processes are slow and are weakly reflected in the terrain. However, the situation changes radically if the vegetation cover integrity is violated, which is inevitable with the modern methods of developing northern territories. Furthermore, global changes in average annual temperatures and the occurrence of karst processes may be the reason behind the development of erosion processes. The authors suggest a method for determining territories with a varying occurrence probability of erosional processes, based on digital elevation modelling. The territory of the Pinezhsky Nature Reserve (Arkhangelsk region) was chosen as the test plot. Direct field studies were previously used to detect exogenous geological processes in this territory. The authors were the first to suggest digital elevation modelling as a method that allows determining the potential danger of erosion in karst landscapes of the northern taiga. The geomorphometric studies resulted in the determination of areas with the greatest and lowest occurrence probability of erosion processes in the Pinezhsky Nature Reserve. It was established that the most significant erosion type was linear erosion, represented by incised river valleys and karst ravines. Sheet erosion is less significant and occurs as sinkholes, local declines, and chasms over the valleys of subterranean rivers.     

Response of BITS (a benthic index based on taxonomic sufficiency) to water and sedimentary variables and comparison with other indices in three Adriatic lagoons

The European Water Framework Directive (WFD, 2000/60/EC) recommends the development of biotic indices for assessing the ecological quality status of water bodies. The Benthic Index based on Taxonomic Sufficiency (BITS) was specifically developed for lagoonal systems, according to the tolerant/opportunistic approach. Macrobenthic data, variables indicative of eutrophication and variables indicative of sedimentary organic matter quality were collected during 18 surveys carried out between 2004 and 2005 in three Adriatic coastal lagoons (Venice Lagoon, Sacca di Goro, Lesina Lagoon). The relationship between environmental variables and biotic indices (AMBI, BENTIX, BITS, BOPA and FINE) was tested using multivariate analyses. Indices based on species classification level appeared to relate better with the variables describing organic matter quality, whereas BITS, which is based on family classification level, seemed related to eutrophication indicative variables, such as sulphide, ammonium, dissolved oxygen and orthophosphate concentrations. The BITS approach reduces the costs associated with sorting and identification of organisms. Providing a rapid assessment of ecological quality, and producing an ecologically relevant classification, BITS seems a promising tool for monitoring programs of Adriatic lagoonal ecosystems. Its sensitivity in reflecting the field conditions elsewhere, however, remains to be assessed.     

Environmental and political implications of Vietnam's water vulnerabilities: A multiscale assessment

Vietnam's low‐lying areas of the Lower Mekong Basin are prone to floods, salt water inundation, and riparian competition with upstream neighbours. Vietnam's opening to the global economy, accompanied by industrialization and a rapidly growing population, impose multiscale (global, regional, local) stresses on urban and rural water systems resulting in water contamination and groundwater overdraft. Water vulnerability is a function of both natural and social hazards and depends on the scope of capital investment, political and ideological institutions, managerial capacity and governance. Water distribution and riparian ecosystem health are also hydropolitical issues related to dam‐building activity by Vietnam and its transboundary neighbours, Laos, Cambodia and particularly China, whose territory contains the source of the Mekong River. A multiscale assessment of Vietnam's interlinked water vulnerabilities indicates that the resilience of the country's social‐ecological water system rests on peaceful resolution of regional transboundary conflicts based on shared economic interests and on improved managerial practices of local authorities.     

Grain boundary and volume diffusion experiments in yttrium aluminium garnet bicrystals at 1,723 K: a miniaturized study

Yb-Y inter-diffusion along a single grain boundary of a synthetic yttrium aluminium garnet (YAG) bicrystal has been studied using analytical transmission electron microscopy (ATEM). To investigate the diffusion, a thin-film containing Yb as the diffusant was deposited perpendicular to the bicrystal grain boundary by pulsed laser deposition (PLD). Structural properties and their change with time in both the diffusant source and the grain boundary are reported. The diffusion profiles are incorporated in a numerical diffusion model, which is applied to determine the grain boundary diffusion coefficient, D _gb , at 1.723 K it is equal to 3 × 10⁻¹⁵ m²/s. We find that grain boundary diffusion is 4.85 orders of magnitude faster than volume diffusion, which was determined from the same diffusion experiment. This result is discussed in the context of special versus general grain boundaries. Finally, we successfully tested the capability of synchrotron-based nano-X-ray fluorescence analysis to map micro-chemical patterns in two dimensions with sub-micrometre resolution.     

Magma evolution beneath Bequia,Lesser Antilles,deduced from petrology of lavas and plutonic xenoliths

Extrusive and intrusive igneous rocks represent different parts of a magmatic system and ultimately provide complementary information about the processes operating beneath volcanoes. To shed light on such processes, we have examined and quantified the textures and mineral compositions of plutonic and cumulate xenoliths and lavas from Bequia, Lesser Antilles arc. Both suites contain assemblages of iddingsitized olivine, plagioclase, clinopyroxene and spinel with rare orthopyroxene and ilmenite. Mineral zoning is widespread, but more protracted in lavas than xenoliths. Plagioclase cores and olivine have high anorthite (An?≤?98) and low forsterite (Fo?≤?84) compositions respectively, implying crystallisation from a hydrous mafic melt that was already fractionated. Xenolith textures range from adcumulate to orthocumulate with variable mineral crystallisation sequences. Textural criteria are used to organize the xenoliths into six groups. Amphibole, notably absent from lavas, is a common feature of xenoliths, together with minor biotite and apatite. Bulk compositions of xenoliths deviate from the liquid line of descent of lavas supporting a cumulate origin with varying degrees of reactive infiltration by evolved hydrous melts, preserved as melt inclusions in xenolith crystals. Volatile saturation pressures in melt inclusions indicate cumulate crystallization over a 162–571 MPa pressure range under conditions of high dissolved water contents (up to 7.8 wt% H₂O), consistent with a variety of other thermobarometric estimates. Phase assemblages of xenoliths are consistent with published experimental data on volatile-saturated low-magnesium and high-alumina basalts and basaltic andesite from the Lesser Antilles at pressures of 200–1000 MPa, temperatures of 950–1050 °C and dissolved H₂O contents of 4–7 wt%. Once extracted from mid-crustal mushes, residual melts ascend to higher levels and undergo H₂O-saturated crystallization in shallow, pre-eruptive reservoirs to form phenocrysts and glomerocrysts. The absence of amphibole from lavas reflects instability at low pressures, whereas its abundance in xenoliths testifies to its importance in mid-crustal differentiation processes. A complex, vertically extensive (6 to at least 21 km depth) magmatic system is inferred beneath Bequia. Xenoliths represent fragments of the mush incorporated into ascending magmas. The widespread occurrence of evolved melts in the mush, but the absence of erupted evolved magmas, in contrast to islands in the northern Lesser Antilles, may reflect the relative immaturity of the Bequia magmatic system.     

Modeling the effects of the variability of temperature-related dynamic viscosity on the thermal-affected zone of groundwater heat-pump systems

Thermal perturbation in the subsurface produced in an open-loop groundwater heat pump (GWHP) plant is a complex transport phenomenon affected by several factors, including the exploited aquifer’s hydrogeological and thermal characteristics, well construction features, and the temporal dynamics of the plant’s groundwater abstraction and reinjection system. Hydraulic conductivity has a major influence on heat transport because plume propagation, which occurs primarily through advection, tends to degrade following conductive heat transport and convection within moving water. Hydraulic conductivity is, in turn, influenced by water reinjection because the dynamic viscosity of groundwater varies with temperature. This paper reports on a computational analysis conducted using FEFLOW software to quantify how the thermal-affected zone (TAZ) is influenced by the variation in dynamic viscosity due to reinjected groundwater in a well-doublet scheme. The modeling results demonstrate non-negligible groundwater dynamic-viscosity variation that affects thermal plume propagation in the aquifer. This influence on TAZ calculation was enhanced for aquifers with high intrinsic permeability and/or substantial temperature differences between abstracted and post-heat-pump-reinjected groundwater.

     

Numerical reconstruction of trajectory of small-size surface drifter in the Mediterranean sea

In this study, we addressed the effects of wind-induced drift on Lagrangian trajectories of surface sea objects using high-resolution ocean forecast and atmospheric data. Application of stochastic Leeway model for prediction of trajectories drift was considered for the numerical reconstruction of the Elba accident that occurred during the period 21.06.2009–22.06.2009: a person on an inflatable raft was lost in the vicinity of the Elba Island coast; from the initial position, the person on a raft drifted southwards in the open sea and later he was found on a partially deflated raft during rescue operation. For geophysical forcing, we used high-resolution currents from the Mediterranean Forecasting System and atmospheric wind from the European Centre for Medium-Range Weather Forecasts. To investigate the effect of wind on trajectory behavior, numerical simulations were performed using different categories of drifter-like particles similar to a person on an inflatable raft. An algorithm of spatial clustering was used to differentiate the most probable search areas with a high density of particles. Our results showed that the simulation scenarios using particles with characteristics of draft-limited sea drifters provided better prediction of an observed trajectory in terms of the probability density of particles.