DFT study of the cation arrangements in the octahedral and tetrahedral sheets of dioctahedral 2:1 phyllosilicates

Quantum mechanical calculations based on the density functional theory (DFT) are used to study the crystal structures of dioctahedral 2:1 phyllosilicates. The isomorphous cation substitution is investigated by exploring different substitutions of octahedral Al³⁺ by Mg²⁺ or Fe³⁺, tetrahedral substitution of Si⁴⁺ by Al³⁺, and different interlayer cations (IC) (Na⁺, K⁺, Ca²⁺, and Mg²⁺). Samples with different kinds of layer charges are studied: only tetrahedrally charged, only octahedrally charged, or mixed octahedral/tetrahedral charged. The effect of the relative arrangements of these substitutions on the lattice parameters and total energy is studied. The experimental observation of segregation tendency of Fe³⁺ and dispersion tendency of Mg²⁺ in the octahedral sheet is reproduced and explained with reference to the relative energies of the octahedral cation arrangements. These energies are higher than those due to the IC/tetrahedral and IC/octahedral relative arrangements. The tetrahedral and octahedral substitutions that generate charged layers also tend to be dispersed. The octahedral cation exchange potentials change with the IC-charge/ionic radius value.     

Magnetic fabric study of the SE Rhenohercynian Zone (Bohemian Massif): Implications for dynamics of the Paleozoic accretionary wedge

The progressive deformation recorded in the magnetic fabric of sedimentary rocks was studied in the SE Rhenohercynian Zone (RHZ), eastern margin of the Bohemian Massif, Czech Republic. Almost 800 oriented samples of the Lower Carboniferous mudstones and graywackes were collected from the SSE part of the Czech RHZ, so-called the Drahany Upland. The anisotropy of magnetic susceptibility (AMS) is predominantly controlled by the preferred orientation of paramagnetic phyllosilicates, mainly iron-bearing chlorites. A regional distribution of the magnetic fabric within the Drahany Upland revealed an increasing deformation from the SSE to the NNW. In the SE, the magnetic fabric is bedding-parallel with magnetic lineation scattered in the bedding plane or trending N–S to NNE–SSW. Further to the NW, the magnetic foliation rotates from the bedding-parallel orientation to the orientation parallel to the evolving cleavage. This rotation is accompanied by a decrease of the anisotropy degree and the prolate nature of the anisotropy ellipsoids. The magnetic lineation is parallel to the strike of the bedding, bedding/cleavage intersection, pencil structure or the fold axes on a regional scale. In the NW part of the Drahany Upland, the magnetic foliation becomes parallel to the cleavage accompanied by an increase of the anisotropy degree and the oblate nature of the anisotropy ellipsoids. The increasing trend of deformation corresponds to the SSE–NNW increase in the degree of anchimetamorphism; both trends being oblique to the main lithostratigraphic formations as typically observed in the sedimentary rocks of the accretionary wedges. The SSE–NNW increase in deformation and anchimetamorphism continues to the Nízký Jeseník Mts., representing the northern part of the same accretionary wedge. The kinematics of deformation could not be unambiguously assessed. The observed magnetic fabric may reflect either lateral shortening or horizontal simple shear or a combination of both mechanisms. Regarding the subduction process, it seems that the sedimentary sequences of the Drahany Upland were subducted, partly offscraped and accreted frontally or partly underplated as opposed to the Nízký Jeseník Mts. where some return flow must have occurred.     

Nocturnal CO2 exchange over a tall forest canopy associated with intermittent low-level jet activity

Summary Nocturnal eddy-covariance carbon dioxide fluxes have uncertainties arising from non-stationary atmospheric processes. Low-level jets (LLJ) are one of the prominent nocturnal boundary-layer phenomena observed over non-mountainous terrain, and are capable of generating shear and turbulence close to the ground. The influence of intermittent LLJ activity on nocturnal carbon dioxide exchange measurements is investigated using wind profile observations and eddy-covariance flux measurements over a tall forest canopy. Results suggest that the buildup and venting of CO₂ are closely associated with LLJ activity during the night. Of significance in quantifying nocturnal fluxes, this paper demonstrates how low-level jet activity introduces sporadic coupling between the canopy and the atmosphere.     

Modelling Regional Climate Change Effects On Potential Natural Ecosystems in Sweden

This study aims to demonstrate the potential of a process-based regional ecosystem model, LPJ-GUESS, driven by climate scenarios generated by a regional climate model system (RCM) to generate predictions useful for assessing effects of climatic and CO₂ change on the key ecosystem services of carbon uptake and storage. Scenarios compatible with the A2 and B2 greenhouse gas emission scenarios of the Special Report on Emission Scenarios (SRES) and with boundary conditions from two general circulation models (GCMs) – HadAM3H and ECHAM4/OPYC3 – were used in simulations to explore changes in tree species distributions, vegetation structure, productivity and ecosystem carbon stocks for the late 21st Century, thus accommodating a proportion of the GCM-based and emissions-based uncertainty in future climate development. The simulations represented in this study were of the potential natural vegetation ignoring direct anthropogenic effects. Results suggest that shifts in climatic zones may lead to changes in species distribution and community composition among seven major tree species of natural Swedish forests. All four climate scenarios were associated with an extension of the boreal forest treeline with respect to altitude and latitude. In the boreal and boreo-nemoral zones, the dominance of Norway spruce and to a lesser extent Scots pine was reduced in favour of deciduous broadleaved tree species. The model also predicted substantial increases in vegetation net primary productivity (NPP), especially in central Sweden. Expansion of forest cover and increased local biomass enhanced the net carbon sink over central and northern Sweden, despite increased carbon release through decomposition processes in the soil. In southern Sweden, reduced growing season soil moisture levels counterbalanced the positive effects of a longer growing season and increased carbon supply on NPP, with the result that many areas were converted from a sink to a source of carbon by the late 21st century. The economy-oriented A2 emission scenario would lead to higher NPP and stronger carbon sinks according to the simulations than the environment-oriented B2 scenario.     

Injection-extraction treatment well pairs: an alternative to permeable reactive barriers

Two of the biggest drawbacks of using permeable reactive barriers (PRBs) to treat contaminated ground water are the high capital cost of installation, particularly when the contaminated ground water is deep below ground surface, and the uncertainty of whether or not PRBs remain effective for the long time scales (e.g., decades) needed for many contaminant plumes. The use of an injection-extraction treatment well pair (IETWP) for capture and treatment of contaminated ground water can circumvent these difficulties, while still providing many of the same advantages offered by PRBs. In this paper, the hydraulics of IETWPs and PRBs are compared, focusing primarily on the width of the captured plume. It is demonstrated that IETWPs act as hydraulic barriers in a manner similar to PRBs, and that IETWPs provide excellent plume capture. A mathematical expression is presented for the plume capture width of an IETWP oriented perpendicular to the ground water flow direction in a homogeneous aquifer. Also discussed are other practical considerations that might determine whether an IETWP is better suited than a PRB for a particular contaminated site; these considerations include operating and maintenance costs, and the conditions under which an IETWP system can be used for in situ remediation.     

In-situ Measurements of Tropospheric Hydroxyl Radicals by Folded Long-Path Laser Absorption During the Field Campaign POPCORN

Absolutely calibrated in-situ measurements of tropospheric hydroxyl radicals, formaldehyde, sulfur dioxide, and naphthalene (C10H8) were performed by long-path laser absorption spectroscopy during the field campaign POPCORN. The absorption light path was folded into an open optical multiple reflection cell with a mirror separation of 38.5 m. Using a light path length of 1848 m and an integration time of 200 s, the average 1-detection limits of OH, HCHO, SO2 and C10H8 during POPCORN were 8.7 · 105 cm–3, 8.3 · 109 cm–3, 2.4 · 109 cm–3, 1.5 · 108 cm–3, respectively. In total, 392 identifications of OH in air spectra were made in a rural environment between August 5 and August 23, 1994. We present and discuss OH absorption spectra and diurnal OH concentration profiles of three days which are representative for measurements under different pollution conditions during POPCORN. The observed maximum and median OH radical concentrations are 1.3 · 107 OH/cm3 and 4.0 · 106 OH/cm3, respectively. The measured diurnal variation of the OH concentration shows a good correlation with the primary formation reaction of OH radicals which is the photolysis of ambient ozone. Deviations from this correlation in the morning and evening hours, when the OH concentration is higher than expected from the ozone photolysis, demonstrate the importance of other photochemical HOx production pathways during POPCORN.     

Gaseous and Particulate Oxidized and Reduced Nitrogen Species in the Atmospheric Boundary Layer in Scandinavia in Spring

Observations of the concentration of several nitrogen containing compounds at five rural Scandinavian sites during March–June 1993 are reported. Total nitrate (NO ₃ ^- + HNO₃) and total ammonium (NH ₄ ⁺ + NH₃) were measured by denuder and filter pack. In general the methods agree well. At all sites the particulate fraction dominated, with the largest fraction of NO ₃ ^- and the lowest of NH ₄ ⁺ at the sites which were closest to the emission sources. The fraction of NO ₃ ^- of total nitrate increased with increasing NO₂ concentrations, indicating that the nighttime conversion of NO₂ to NO ₃ ^- is an important route of formation for NO ₃ ^- . A positive correlation was found between HNO₃ and O₃ in June at all sites, while no correlation was found early in the spring. Model calculations were made with a lagrangian boundary layer photooxidant model for the whole period, and compared to the measured concentrations. The calculated ratio between mean observed and modelled daily maximum concentrations of ozone over the measurement period were within +/–10% at all sites. The models ability to describe the daily ozone maximum concentration was satisfactory with an average deviation of 19–22% from the observed concentrations. HNO₃ was underestimated by over 50% at all sites except the one closest to the emission sources. The correlation between modelled and observed concentrations was generally best for the sites with shortest transport distance from the sources of emission.