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.     

Bayesian approach to daily rainfall modelling to estimate monthly net infiltration using the Thornthwaite water budget and Curve Number methods

The Thornthwaite and Mather water budget is a simple and frequently applicable tool to estimate surpluses of water, which are not stored in the soil profile. Combining it with the empiric CN-method of the US Soil Conservation Service (US-SCS), which is applied to daily rainfall records, it is possible to estimate the runoff, and this way, from the difference between surpluses and runoff, to estimate the net infiltration that would recharge a phreatic aquifer. In order to apply both methods during a sequence of years, it is necessary to predict the number of rain events per month, and the rainfall depth for each event. In this work, the author proposes a methodology based on the theorem of Bayes to estimate the number of occurrences of rainy events in a considered month conditioning the forecast to the monthly rainfall. In addition, an exponential distribution to generate rainfall depth knowing the monthly rainfall was done. Both algorithms were applied in four stations of the southern region of Santa Fe province (Argentina). More than 7,600 forecasts of rain occurrences and rainfall depths were compared with the observed records. Moreover, the runoff values estimated by means of the US-SCS method, using the observed rainfall and using rainfalls predicted with the algorithms were also compared. In both cases, the obtained results were also very satisfactory. The proposed methodologies allow the correct application of the balance of Thornthwaite and Mather together with the US-SCS method and a good forecast of monthly runoff and net infiltration.     

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.     

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.