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.     

The lunar geochemistry of chromium and vanadium

Crystal/liquid partition coefficients for Cr, V, Mn, and Fe have been determined experimentally between olivine, orthopyroxene, clinopyroxene and silicate melt possesing the composition of a primitive lunar green glass, at oxygen fugacities appropriate to the lunar interior. These species all behave essentially as compatible elements and possess crystal/liquid partition coefficients mostly between 0.3 and 0.9. Partition coefficients for Cr, V, and Mn are generally similar to those of Fe. This implies that crystal/liquid fractionation processes in the lunar interior which do not involve the participation of spinels would not have been effective in fractionating MnO, CrO, and VO from FeO. The well-known constancy of FeO/MnO ratios in nearly all lunar rocks is a reflection of this behaviour. It is shown that comparably strong correlations between CrO-;FeO and VO-;FeO exist for lunar highland breccias and soils from all sites and that these correlations extend to primitive lunar volcanic glasses associated with mare volcanism, strongly suggesting that the CrO/FeO and VO/FeO ratios so derived are of global importance. The observed ratios characterizing differentiated regions of the Moon can be combined with the corresponding ratios for residual refractory portions of the Moon, using measured partition coefficients for Fe, Mg, Cr, V, and Mn between olivine, orthopyroxene and liquid. Bulk Moon abundances for Cr and V have been calculated for a range of reasonable assumptions concerning the petrogenetic relationships between differentiated portions of the Moon and complementary refractory residua consisting of olivine and orthopyroxene mineralogies. Because of the small differences in crystal liquid partition coefficients between FeO, CrO, and VO, these estimates are insensitive to large variations in the models. The bulk Moon is accordingly estimated to contain 2190–2463 ppm Cr and 79–95 ppm V. These values are very similar to the Cr and V contents of the Earth's mantle, estimated as 3010 ppm Cr and 81 ppm V by Sun (1982). The geochemical implications of these similarities are discussed.     

Morphological analysis of the drainage system in the Eastern Alps

We study the morphology of the major rivers draining the Eastern Alps to test whether the active tectonics of this part of the orogen is reflected in the shape of channel profiles of the river network. In our approach we compare channel profiles measured from digital elevation models with numerically modelled channel profiles using a stream power approach. It is shown that regions of high stream power coincide largely with regions of highest topography and largest uplift rates, while the forelands and the Pannonian Basin are characterised by a significantly lower stream power. From stream power modelling we conclude that there is young uplift at the very east of the Eastern Alps, in the Bohemian Massif and in the Pohorje Range. The impact of the Pleistocene glaciations is explored by comparing properties of rivers that drain in proximal and distal positions relative to the ice sheet during the last glacial maximum. Our analysis shows that most knick points, wind gaps and other non-equilibrium features of catchments covered by ice during the last glaciations (Salzach, Enns) can be correlated with glacial processes. In contrast the ice free catchments of the Mur and Drava are characterized by channels in morphological equilibrium at the first approximation and are showing only weak evidence of the strong tectonic activity within these catchments. Finally, the channel profiles of the Adige and the divide between the upper Rhine and Danube catchments differ significantly from the other catchments. We relate this to the fact that the Adige and the Rhine respond to different base levels from the remainder of the Eastern Alps: The Adige may preserve a record from the Messininan base level change and the Rhine is subject to the base level lowering in the Rhine Graben.     

The carbon isotopic response of algae, (cyano)bacteria, archaea and higher plants to the late Cenomanian perturbation of the global carbon cycle: Insights from biomarkers in black shales from the Cape Verde Basin (DSDP Site 367)

The stable carbon isotopic compositions of free and sulfur (S)-bound biomarkers derived from algae, (cyano)bacteria, archaea and higher plants and total organic carbon (TOC) during the first phase of the late Cenomanian/Turonian oceanic anoxic event (OAE) were measured in black shales deposited in the southern proto-Atlantic Ocean in the Cape Verde basin (DSDP Site 367) to determine the response of these organisms to this major perturbation of the global carbon cycle resulting from widespread burial of marine organic matter. The average positive isotope excursions of TOC and biomarkers varied from 5.1‰ to 8.3‰. The δ¹³C values were cross correlated to infer potential common sources of biomarkers. This revealed common sources for C₃₁ and C₃₂ hopanes but no 1:1 relationship for pristane and phytane. The correlation of δ¹³C_TOC with the δ¹³C value of sulfur (S)-bound phytane is the strongest. This is because S-bound phytane is derived from phytol that originates from all marine primary producers (algae and cyanobacteria) and thus represents a weighted average of their carbon isotopic compositions. The δ¹³C values of S-bound phytane and C₃₅ hopane were also used to estimate pCO₂ levels. Before the OAE burial event, pCO₂ levels are estimated to be ca. 1300 ppmv using both biomarkers and the independent maximum Rubisco fractionation factors. At times of maximum organic carbon burial rates during the OAE, reconstructed pCO₂ levels are estimated to be ca. 700 ppmv. However, compared to other C/T OAE sections the positive isotope excursion of S-bound phytane is also affected by an increased production during the OAE. When we compensate for this, we arrive at pCO₂ levels around 1000 ppmv, a reduction of ca. 25%. This indicates that burial of organic matter can have a large effect on atmospheric CO₂ levels.     

Thermal stability of ladderane lipids as determined by hydrous pyrolysis

Anaerobic ammonium oxidation (anammox) has been recognized as a major process resulting in loss of fixed inorganic nitrogen in the marine environment. Ladderane lipids, membrane lipids unique to anammox bacteria, have been used as markers for the detection of anammox in marine settings. However, the fate of ladderane lipids after sediment burial and maturation is unknown. In this study, anammox bacterial cell material was artificially matured by hydrous pyrolysis at constant temperatures ranging from 120 to 365 °C for 72 h to study the stability of ladderane lipids during progressive dia- and catagenesis. HPLC-MS/MS analysis revealed that structural alterations of ladderane lipids already occurred at 120 °C. At temperatures >140 °C, ladderane lipids were absent and only more thermally stable products could be detected, i.e., ladderane derivatives in which some of the cyclobutane rings were opened. These diagenetic products of ladderane lipids were still detectable up to temperatures of 260 °C using GC-MS. Thus, ladderane lipids are unlikely to occur in ancient sediments and sedimentary rocks, but specific diagenetic products of ladderane lipids will likely be present in sediments and sedimentary rocks of relatively low maturity (i.e., C₃₁ hopane 22S/(22S + 22R) ratio <0.2 or ββ/(αβ + βα + ββ) ratio of >0.5).     

Numerical modeling for analyzing thermal surface anomalies induced by underground coal fires

Coal seams burning underneath the surface are recognized all over the world and have drawn increasing public attention in the past years. Frequently, such fires are analyzed by detecting anomalies like increased exhaust gas concentrations and soil temperatures at the surface. A proper analysis presumes the understanding of involved processes, which determine the spatial distribution and dynamic behavior of the anomalies.In this paper, we explain the relevance of mechanical and energy transport processes with respect to the occurrence of temperature anomalies at the surface. Two approaches are presented, aiming to obtain insight into the underground coal fire situation: In-situ temperature mapping and numerical simulation. In 2000 to 2005, annual temperature mapping in the Wuda (Inner Mongolia, PR China) coal fire area showed that most thermal anomalies on the surface are closely related to fractures, where hot exhaust gases from the coal fire are released. Those fractures develop due to rock mechanical failure after volume reduction in the seams. The measured signals at the surface are therefore strongly affected by mechanical processes.More insight into causes and effects of involved energy transport processes is obtained by numerical simulation of the dynamic behavior of coal fires. Simulations show the inter-relation between release and transport of thermal energy in and around underground coal fires. Our simulation results show a time delay between the coal fire propagation and the observed appearance of the surface temperature signal. Additionally, the overall energy flux away from the burning coal seam into the surrounding bedrock is about 30-times higher than the flux through the surface. This is of particular importance for an estimation of the energy released based on surface temperature measurements. Finally, the simulation results also prove that a fire propagation rate estimated from the interpretation of surface anomalies can differ from the actual rate in the seam.     

Groundwater flow and contaminant transport modelling at an air weapons range

Numerical modelling was done at the Cold Lake Air Weapons Range, Canada, to test whether the dissolved RDX and nitrate detected in groundwater come from the same sources, and to predict whether contamination poses a threat to the surface water receptors near the site. Military live fire training activities may indeed pose a risk of contamination to groundwater resources, however field investigations on military bases are quite recent, and little information is available on the long-term behaviour of munition residues related contaminants. Very limited information was available about the contaminant source zones, which were assigned based on our knowledge of current training activities. The RDX plume was well represented with the model, but the heterogeneous distribution of nitrate concentrations was more difficult to reproduce. It was nonetheless determined that both contaminants originate from the same areas. According to the model, both contaminants should reach the nearby river, but concentrations in the river should remain very low if the source zone concentration does not change. Finally, the model allowed the recommendation of a new location for the main bombing target, which would offer added protection to the river and the lake into which it flows.     

Phytoreduction and volatilization of mercury by ascorbate in Arabidopsis thaliana, European beech and Norway spruce

Mercury vapor (Hg⁰) emission from plants contributes to the atmospheric Hg cycle. Young barley (Hordeum vulgare L.) plants grown on a hydroponic cultivation medium containing Hg(II) have previously been shown to increase their Hg⁰ emission significantly by reduction of Hg(II) with endogenous ascorbic acid. Regarding the potential contribution to the Hg cycle from the vast forest-covered areas, it was important to investigate this mechanism in trees. The increase in Hg⁰ emission from young European beech plants cultivated on a HgCl₂ medium exceeded that from controls by ca. tenfold and was proportional to the Hg(II) concentration. From these experiments, a flux of 12.8 μg Hg⁰/h/m² was estimated at an exposure of the roots to 20 μM Hg(II). Mercury vapor release from homogenates of Norway spruce needles exceeded that from European beech leaves by a factor of 2.3–4, i.e. in proportion to the reported AA concentrations; the reduction was maximal at alkaline pH which is typical for AA. The 8.4-fold difference in Hg⁰ release between homogenates from wild-type Arabidopsis thaliana and from its AA-deficient mutant vtc 1-1 also paralleled the reported difference in AA levels of both species. It is concluded that the phytoreduction and vaporization of Hg by AA is an important mechanism as much for Hg detoxification in trees as for Hg emission to the atmosphere. The efficiency of this process seems to result from the optimal coordination of transfer and biochemical transformation of mercuric ions and Hg vapor. There is no evidence for a relevant difference in the mechanisms of biogenic Hg(II) reduction between grass plants and trees.