Growth of magnesio-aluminate spinel in thin-film geometry: in situ monitoring using synchrotron X-ray diffraction and thermodynamic model

Polycrystalline spinel layers were grown experimentally at the contacts between single-crystal corundum substrates and initially amorphous, then polycrystalline MgO thin films. The growth behavior of the spinel layers was monitored in situ using synchrotron X-ray diffraction. The change in the integrated intensity of the 111 spinel Bragg peak was correlated with the thickness of the layer as determined from ex situ TEM characterization of the run products. At \(900\,^{\circ }\hbox {C},\) a transition from linear growth, corresponding to interface reaction control, to parabolic growth, corresponding to diffusion control, occurred at a layer thickness of less than 10 nm. At 1,000 \(^{\circ }\hbox {C},\) growth was largely linear up to a layer thickness in excess of 300 nm. A thermodynamic model was applied to extract the kinetic parameters characterizing interface motion and long-range diffusion from this growth behavior.     

Shifts in climate suitability for wine production as a result of climate change in a temperate climate wine region of Romania

Climate change is causing important shifts in the suitability of regions for wine production. Fine scale mapping of these shifts helps us to understand the evolution of vineyard climates, and to find solutions through viticultural adaptation. The aim of this study is to identify and map the structural and spatial shifts that occurred in the climatic suitability for wine production of the Cotnari wine growing region (Romania) between 1961 and 2013. Discontinuities in trends of temperature were identified, and the averages and trends of 13 climatic parameters for the 1961 to 1980 and 1981 to 2013 time periods were analysed. Using the averages of these climatic parameters, climate suitability for wine production was calculated at a resolution of 30 m and mapped for each time period, and the changes analysed. The results indicate shifts in the area’s historic climatic profile, due to an increase of heliothermal resources and precipitation constancy. The area’s climate suitability for wine production was modified by the loss of climate suitability for white table wines, sparkling wines and wine for distillates; shifts in suitability to higher altitudes by about 67 m, and a 48.6% decrease in the area suitable for quality white wines; and the occurrence of suitable climates for red wines at lower altitudes. The study showed that climate suitability for wine production has a multi-level spatial structure, with classes requiring a cooler climate being located at a higher altitude than those requiring a warmer climate. Climate change has therefore resulted in the shift of climate suitability classes for wine production to higher altitudes.     

Changes in the Abundance and Species Composition of Phytoplankton in the Last 150 Years in the Southern Black Sea

Changes in total abundance and in species composition of phytoplankton in the last 150 years in the southern Black Sea were investigated through a paleoecological study of two sediment cores. The results show changes in the species composition and a marked increase in total abundance of siliceous protists after around 1960. In core 22 (42°13.534′ N/36°29.555′ E), the dominating species before 1960 were Cyclotella choctawhatcheeana and Thalassiosira oestrupii. In core 25 (42°6.212′ N/36°37.460′ E), the dominating species before 1960 were T. oestrupii, Cyclotella meneghiniana, C. choctawhatcheeana, and Pseudosolenia cf. calcar-avis. Core 22 was located in closer proximity to the rim current than core 25, and the differences in total abundance between the cores could be related to differences in local nutrient loading prior to 1960. After around 1960, both cores changed to a community dominated by C. choctawhatcheeana. The changes in total abundance and species composition after around 1960 could be related to the increased nutrient loading from the Danube River into the rim current after the late 1960s. The results also showed changes in both total abundance and in species composition of dinoflagellate cysts. The dominating dinoflagellate cysts recorded were Lingulodinium polyedrum, Polykrikos schwartzii, and Spiniferites spp.     

黔北务正道地区铝土矿稀土元素地球化学特征

选取新模向斜的一个钻孔剖面,对铝土矿的矿物组成及稀土元素地球化学特征进行了研究。铝土矿矿石矿物以一水硬铝石为主,另有少量一水软铝石。其次为高岭石、绿泥石等黏土矿物,以及少量重矿物。此外,在含矿岩系近底部还发现有富集Ce元素的矿物氟菱钙铈矿[Ce2Ca(CO3)3F2]。从剖面顶部至底部,铝土矿中稀土元素含量呈逐渐增加的趋势,且稀土元素参数LaN/YbN、LaN/SmN和GdN/YbN的数值均随深度逐渐增大。说明从剖面顶部至底部,稀土元素的淋滤迁出逐渐减弱,且稀土元素间存在一定的分异。稀土元素间的分异可能由不同的含稀土元素矿物抗风化淋滤差异所致。铝土矿稀土元素配分模式表现为LREE明显富集、MREE中等-弱富集、HREE相对平坦的特征,且具有明显的正Ce异常。δCe异常值随深度增加逐渐减小,接近含矿岩系底部,δCe异常值再次增大。含矿岩系上部的Ce异常是由氧化条件下Ce3+向Ce4+转变并形成方铈矿(CeO2)所致。随着深度的增加,含矿岩系的氧化性逐渐减弱,从而δCe异常值逐渐减小。接近含矿岩系底部,由于氟菱钙铈矿[Ce2Ca(CO3)3F2]的形成,导致δCe异常值再次增大。氟菱钙铈矿的沉淀可通过氟化物络合物(CeF2+或CeCO3F0)与Ca2+和HCO3-发生反应来完成。     

Early Cretaceous fish trails from La Rioja, Spain

We report a new find of the fish trail Undichna unisulca in fluvial sediments of the Lower Cretaceous Oliván Group of the Cameros Basin (Aptian-Albian; Valtrujal, La Rioja, northern Spain). It is the second Mesozoic record of Undichna unisulca after the first discovery in the Lower Cretaceous of central Spain (Las Hoyas, Cuenca, central Spain). The trails are characterized by single sinusoidal waves which in this case are often surrounded by well-preserved lateral levees that rule out an undertrail hypothesis.The continental depositional setting, a floodplain fluvial system, reflects the known broad palaeoenvironmental distribution of Undichna and confirms its occurrences in freshwater settings.     

A comparison of brachyuran crab community structure at four mangrove locations under different management systems along the Melaka Straits-Andaman Sea Coast of Malaysia and Thailand

Brachyuran crab community structure was compared between mangrove sites under different management systems from four locations along the Melaka Straits-Andaman Sea Coast. Klong Ngao, a mangrove estuary in Ranong Province of southern Thailand, lies within a Biosphere Reserve designated in 1997. Sites were positioned in plantations at a former charcoal concession forest, a disused tin mine, and an abandoned shrimp pond along this estuary. The Merbok estuary in Kedah, Malaysia, is partially managed: the mangroves are cut for charcoal and poles on a small scale and the forests are left to regenerate naturally. The Matang Mangrove Forest Reserve in Perak, Malaysia, is heavily exploited but well managed, forRhizophora wood to produce charcoal, and has been for 100 years. Sites were positioned in plantations of different ages. Kuala Selangor Nature Park, Selangor, Malaysia, was established as a nature reserve in 1987 and contains mature mangrove forest regenerating naturally from previous selective felling. At Klong Ngao and Matang, mature reserve forest sites were also studied for comparison with plantation sites. The sites included both upstream and downstream locations and were of similar area, minimizing effects from possible species-area relationships. Sites were chosen with similar environmental conditions and with a dominance ofRhizophora spp. At each site per location, the brachyuran crabs were sampled quantitatively in 100 m² quadrats by three independent 15-min timed crab catches. The crab community recorded was analyzed by univariate and multivariate statistical techniques. Management history plays an important role in moderating the crab community structure. The crab community also changes with the age of the mangrove forest stand. Sesarmid crabs consistently dominated in mature forests, whereas young plantations were colonized mainly by ocypodid crabs. The findings show that heavily effected sites—e.g., disused tin mining areas, former concession forests, and abandoned shrimp ponds—can be rehabilitated by planting mangroves and that the crab community is a useful ecological indicator of habitat status.     

Geochemical constraints on the genesis of the Sarıcakaya intrusive rocks,Turkey: Late Paleozoic crustal melting in the central Sakarya Zone

The Sakarya Zone is intruded by several Late Paleozoic granitoids, of which the Sar?cakaya intrusive rocks in the central Sakarya (Eski?ehir) region, is the least-studied. The Sar?cakaya intrusive rocks consist mainly of quartz diorite-granodiorite, granodiorite and granite. They are, geochemically, divided into two groups: diorites and granites. The former is medium-K and calc-alkaline (mainly I-type), whereas the latter is high-K to shoshonite and calcic (I-type). Typical minerals for both rock types are plagioclase, K-feldspar, quartz, biotite, hornblende and Fe–Ti oxides. Chondrite-normalized REE patterns for the Sar?cakaya intrusive rocks are moderately fractionated and have small negative Eu anomalies. They are enriched in LILE and LREE relative to HFSE showing characteristics of arc-related granitoids. Geochemical characteristics of the Sar?cakaya intrusive rocks indicate a hybrid origin through partial melting of lower crustal source rocks.     

Rutile/TiO<Subscript>2</Subscript>II phase equilibria

The transition between rutile and α-PbO₂ structured TiO₂ (TiO₂II) has been investigated at 700–1,200 °C and 4.2–9.6 GPa. Hydrothermal phase equilibrium experiments were performed in the multi-anvil apparatus to bracket the phase boundary at 700, 1,000, and 1,200 °C. The equilibrium phase boundary is described by the equation: P (GPa)=1.29+0.0065 T ( °C). In addition, growth of TiO₂II was observed in experiments at 500 and 600 °C, although growth of rutile was too slow to bracket unambiguously the equilibrium boundary at these temperatures. Water was not detected in either rutile or TiO₂II, and dry synthesis experiments at 1,200 °C were consistent with the phase boundary determined in the fluid-bearing experiments, suggesting that the equilibrium is unaffected by the presence of water. Our bracket of the phase boundary at 700 °C is consistent with the reversed, dry experiments of Akaogi et al. (1992) and the reversals of Olsen et al. (1999). The new data suggest that the phase boundary is linear, in agreement with Akaogi et al. (1992), but in striking contrast to the phase diagram inferred by Olsen et al. (1999). The natural occurrence of TiO₂II requires formation pressures considerably higher than the graphite–diamond phase boundary.     

Line-broadening effects in the powder infrared spectrum of apatite

The crystallinity of natural and synthetic apatite samples is often determined from the broadening of ν ₄ PO₄ infrared absorption bands. However, various physical mechanisms contribute to the observed linewidth. In the present study, the factors determining the linewidth in the powder spectrum of synthetic fluorapatite and hydroxyapatite samples are investigated. The temperature dependence of the infrared spectrum (10–270 K) is used to assess the respective contributions of homogeneous broadening, related to the decay of phonons through anharmonic coupling, and heterogeneous broadening related to elastic strain and macroscopic electrostatic effects. This latter contribution is dominant in the investigated samples and depends on the shape of powder particles. It is discussed under the light of the theoretical modeling of the low-frequency dielectric properties of apatite based on first-principles density functional theory calculations. The linewidth of the weak ν ₁ PO₄ absorption band provides a reliable information on microscopic sources of broadening, i.e., apatite crystallinity. In comparison, the other more intense PO₄ bands are more sensitive to long-range electrostatic effects.