Rigid unit modes in the molecular dynamics simulation of quartz and the incommensurate phase transition

A molecular dynamics simulation of quartz at different temperatures both in the a and in the phase has been conducted. The - phase transition could be observed. A phonon analysis of the -phase confirms and rounds out in a quantitative way the origin of the incommensurate (ic) modulated phase. In particular it traces the optic soft mode at becoming (to a good approximation) a so-called rigid unit mode (RUM) at q0, and elucidates its coupling to the transverse acoustic mode which precipitates the incommensurate transition. This success underpins and illuminates the concept of RUMs and their role in structural phase transitions.     

Streams in the Harz National Parks (Germany) — a hydrochemical and hydrobiological evaluation

Between 1995 and 2001, 16 measuring points at small and medium sized brooks in the Harz National Parks were sampled. The samples have been evaluated by means of hydrochemistry and macroinvertebrate biology. Although nearly all streams are largely uncontaminated by oxygen-consuming substances, they are settled only by a small number of macroinvertebrate species. There is a clear correlation between this number and pH. The reduction in species number with decrease of pH is mainly caused by the absence of most Ephemeroptera, some Coleoptera and Trichoptera. Comparing biological evaluation of acidity with physico-chemical measurements, a unacceptable underestimation was found. The reason could be that different sensitivities to acidification between regional populations seem to exist.

Despite of the low species number, there is a very specific macroinvertebrate fauna that emphasizes the conservation value of the Harz National Parks.     

Verteilung und Wanderung von Neunaugen im Elbeästuar (Deutschland)

From March 1989 until May 1995 overall 675 hauls were performed using a commercial stow net vessel to get information concerning spatial and seasonal distribution, length frequency distribution, stock situation and migration patterns of lampreys in the Elbe estuary in northern Germany.2217 river lampreys (Lampetra fluviatilis) and 10 sea lampreys (Petromyzon marinus) were caught during the whole study period. The river lamprey occurred in 40.3% of the performed stow net hauls. The catch success was highest in the western main channel, whereas the frequency of occurrence of river lampreys was only about 10.9% at the most upstream site in the southern marginal area. In 1989 and 1990 significantly more than 50% of the hauls contained river lampreys. In contrast, from 1991 to 1995 their frequency of occurrence was lower than 40%, in 1991 even lower than 20%. Sea lampreys occurred only at 6 from 9 sampled sites and were only observed in 1990 and 1992-1994.Total lengths of river lampreys varied between 7 and 46 cm. Based on the length frequency distribution, the following three size classes of river lampreys were separated: LF I (7 to 16 cm), LF II (17-26 cm) and LF III (27-46 cm). The majority of the caught individuals could be grouped in size class LF III. Total lengths of sea lampreys ranged between 69 and 85 cm and were restricted to only one size class (PM III).70% of all sea lampreys were caught in April and May. Most of the sea lampreys were observed in the eastern main channel. The maximum average abundance of river lampreys was observed with 6.75 Ind · m⁻³ · 10⁻⁶ in the same area in 1992. However, in 1993 and 1994 the highest average abundances of river lampreys occurred in the western main channel.Based on redundance analysis, a significant correlation between the abundances of lampreys and the environmental variables autumn, spring, summer, salinity, water temperature, grain size, new moon and first moon quarter was found. The downstream migrating river lampreys of size class LF I und the sea lampreys during their anadromous spawning migration showed highest abundances mainly in spring, whereas high abundances of river lampreys of size class LF II in the feeding phase occurred in summer. The presence of both size classes LF I and LF II confirms the successful reproduction of river lampreys in the catchment area of the Elbe. The observation of river lampreys of size class LF III during their anadromous spawning migration was closely correlated with the variable autumn. A spring spawning migration of river lampreys was not observed.     

Towards the establishment of a reliable proxy for the reactive surface area of smectite

Reactive surface area is one of the key parameters for studying the kinetics of mineral dissolution. The common practice in experimental kinetics is to normalize the dissolution rate to the surface area measured by the BET method. The relationship between BET surface area and the reactive surface area is not trivial in minerals such as smectites, which possess both internal and external surface areas, and in which the dissolution is controlled by the chemical attack on the edge surface. The present study examines two proxies for the reactive surface area of the Clay Mineral Society reference smectite SAz-1: BET surface area and the edge surface area measured using AFM.Since smectites are very microporous, their BET surface area is strongly influenced by the degassing procedure. It is demonstrated that outgassing the smectite powder at 135°C in a 15 mL min⁻¹ N₂ gas flow for at least 24 hours minimizes contribution from micropores to less than 11% of the BET surface area.Following dissolution experiments in solutions with a low electrolyte concentration, the BET surface area increased from 34 ± 2 m² g⁻¹ in raw SAz-1 to 127 ± 13 m² g⁻¹ in SAz-1 sample recovered from dissolution experiments. This increase in BET surface area is explained by a decrease in the average size of the smectite aggregates, and by an increase in microporosity due to the depletion in the major interlayer cation, i.e., Ca²⁺. As the BET surface area of the raw smectite sample includes considerably less microporosity compared to the BET surface area of the smectite recovered from dissolution experiments, the former is a better approximation of the external surface area of the dried sample powder.AFM measurements show that there is no correlation between the specific external surface area of the sample and its specific edge surface area. This observation is explained by the platy morphology of the smectite particle in which the specific external surface area depends linearly on the height reciprocal, whereas the specific edge surface area is independent of the particles height and depends linearly on the sum of the reciprocals of the length of the axes. Therefore, there is no reason to expect a correlation between the BET and the edge surface area. Our results show that the edge surface area (4.9 ± 0.7 m² g⁻¹) of the smectite particles cannot be predicted based on its external surface area (136 ± 20 m² g⁻¹). Therefore, the BET surface area cannot serve as a proxy for the reactive surface area. We suggest using AFM measurements of the specific edge surface area as an alternative proxy for the reactive surface area of smectite.     

The solubility of [4H]Si defects in α-quartz and their role in the formation of molecular water and related weakening on heating

The nature of the solubility of water as [4H]_Si defects in quartz, and their role in providing a source of molecular water on heating, is investigated. Existing ab inito energy calculations on the incorporation of water in quartz are used to show that energetically 4H for Si substitution is likely to constitute the most prevalent mode of water uptake on the atomic scale in quartz under equilibrium conditions, and that the planar defects previously observed by a number of different authors by electron microscopy in wet quartz are likely to be planar rafts of aggregated [4H]_Si defects which are formed on supersaturation. These new conclusions call into question the previous identification of the planar defects as high pressure water clusters and require that their role in the production of molecular water in the context of recent theories of hydrolytic weakening be re-assessed. Accordingly the existing ab initio results have been used to establish the characteristics of the phase diagram for the system quartz-water in the temperature and pressure range of interest in hydrolytic weakening. Additional electron-optical experiments on wet quartz show that, on annealing at temperature in the electron microscope, similar planar defects develop in wet quartz by a diffusion process. In the context of existing theories of hydrolytic weakening it is now proposed that the conversion of [4H]_Si defects to molecular water, where this is dictated by the equilibrium phase diagram, leads to a relatively large increase in volume and to the appearance of the bubbles of free water and the nucleation of associated prismatic dislocation loops of Burgers vector b=1/3 a $\langle 11\bar 20\rangle $ as previously observed. Ultimately the development of these loops leads to dislocation-induced plasticity.     

Vegetation and climate changes in northwestern Russia during the Lateglacial and Holocene inferred from the Lake Ladoga pollen record

The new pollen record from the upper 12.75 m of a sediment core obtained in Lake Ladoga documents regional vegetation and climate changes in northwestern Russia over the last 13.9 cal. ka. The Lateglacial chronostratigraphy is based on varve chronology, while the Holocene stratigraphy is based on AMS ¹⁴C and OSL dates, supported by comparison with regional pollen records. During the Lateglacial (c. 13.9–11.2 cal. ka BP), the Lake Ladoga region experienced several climatic fluctuations as reflected in vegetation changes. Shrub and grass communities dominated between c. 13.9 and 13.2 cal. ka BP. The increase in Picea pollen at c. 13.2 cal. ka BP probably reflects the appearance of spruce in the southern Ladoga region at the beginning of the Allerød interstadial. After c. 12.6 cal. ka BP, the Younger Dryas cooling caused a significant decrease in spruce and increase in Artemisia with other herbs, indicative of tundra‐ and steppe‐like vegetation. A sharp transition from tundra‐steppe habitats to sparse birch forests characterizes the onset of Holocene warming c. 11.2 cal. ka BP. Pine forests dominated in the region from c. 9.0 to 8.1 cal. ka BP. The most favourable climatic conditions for deciduous broad‐leaved taxa existed between c. 8.1 and 5.5 cal. ka BP. Alder experiences an abrupt increase in the local vegetation c. 7.8 cal. ka BP. The decrease in tree pollen taxa (especially Picea) and the increase in herbs (mainly Poaceae) probably reflect human activity during the last 2.2 cal. ka. Pine forests have dominated the region since that time. Secale and other Cerealia pollen as well as ruderal herbs are permanently recorded since c. 0.8 cal. ka BP.     

Plate and intraplate processes of Hercynian Europe during the late paleozoic

It is speculated that until Late Carboniferous time the region of Hercynian Europe was occupied by an elongated island arc system underlain by a segment of continental crust. In the Upper Carboniferous, two subduction zones are assumed to have extended from the north and south beneath Hercynian Europe. An extensive zone of hot, partially molten upper mantle lay above and between these, and diapiric uprise of portions of this material led to separation of mafic magmas, widespread partial melting in the lower and middle crust, high temperature-low pressure metamorphism in crustal rocks, and regional uplift and extension of the crust, as indicated by intermontane troughs and their associated volcanic rocks.In Visean to Westphalian time Hercynian Europe collided with both the large neighbouring plates North America-Europe and Africa. During these diachronous collisions and owing to reduced rigidity of the relatively hot island arc crust, the irregular continental margins of the larger and thicker continental plates induced oroclinal bending of Hercynian Europe. After the collision processes had been terminated, processes of upper mantle activity continued, causing further crustal uplift and even, enhanced crustal extension for several tens of million years into the Lower Permian. Decline of the upper mantle activity beneath Hercynian Europe is indicated by crustal subsidence and formation of a peneplain in Permian time followed by the Upper Permian transgression of both the Zechstein sea and the Tethys sea which mark the end of the Hercynian geodynamic cycle.