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.     

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.     

Kornerupine parageneses in whiteschists and other magnesian rocks: is kornerupine + talc a high-pressure assemblage equivalent to tourmaline + orthoamphibole?

Kornerupine, (□,Fe,Mg)(Mg,Fe,Al)₉(Si,Al,B)₅ (O,OH,F)₂₂, has been reported with talc in rocks from six localities worldwide, but only at Chilapila Hill in the Lufilian Arc, Zambia do textural relationships imply that kornerupine (Krn) equilibrated with talc (Tlc) during a prograde metamorphic event at T≈ 640 °C, P≈ 13 kbar; a prograde Krn + Tlc assemblage has also been reported from Mautia Hill, Tanzania (P ≤ 13 kbar). In order to estimate possible constraints on the stability range for the kornerupine + talc paragenesis in nature, we constructed a P-T diagram in the model system MgO-Al₂O₃-SiO₂-H₂O (MASH) for seven phases quartz (Qtz), B-free kornerupine sensu stricto, anthophyllite (Ath), chlorite (Chl), cordierite (Crd), kyanite (Ky), and talc. The minimum pressure for Krn + Tlc + Ky stability in MASH is close to that for Ky + Tlc stability, i.e., 6–8 kbar, at T≤ 780 °C. However, in the natural system, B₂O₃ and Na₂O are major constituents in Krn and orthoamphibole (Oam), respectively, and dravitic tourmaline (Tur) is widespread. The critical assemblage alternative to Krn + Tlc in nature is Tur + Oam. The upper pressure limit of Tur + Ath is determined by the upper pressure for anthophyllite: 7.7–10.5 kbar at 682–794 °C in the MgO-SiO₂-H₂O system (Chernosky et al. 1985, Am Mineral 70:223–236), and is undoubtedly higher in the presence of Na₂O, CaO, and Al₂O₃. At three of the six localities, talc is a retrograde phase; nonetheless, it possibly equilibrated with kornerupine on the retrograde path or during a later metamorphic event at P-T conditions appropriate for Ky + Tlc. At the sixth locality (Mulvoj, southwestern Pamir Mountains, Tajikistan), Krn is found in the same thin section as talc and kyanite and all three minerals formed during a prograde metamorphic event at T≥ 650 °C, P near 7 kbar. However, Krn is restricted to a lens 4 to 6 mm thick of phlogopite + anthophyllite + Tur and it does not touch either talc or kyanite. A reaction relating the Mulvoj and Chilapila Hill (Krn + Tlc + Ky + Qtz + Tur) parageneses is calculated from compositions in the Mulvoj rock to be 0.40Tur + 2.55Ath + 1.33H₂O + 0.27F = Krn + 2.16Tlc + 0.36B₂O₃ + 0.02Rutile + 0.19Na₂O + 0.17CaO. Given the difference in metamorphic pressures estimated for Mulvoj and Chilapila Hill, Krn + Tlc is inferred to be favored by increasing pressure as well as by low Na₂O and CaO contents. Some FeO, F, Fe₂O₃, and BeO are present in measurable amounts in at least one of the phases in the Mulvoj and Chilapila Hill whiteschists (e.g., Krn contains 0.24–0.67 wt% BeO), but the effect of these constituents is subordinate to that of Na₂O, CaO and B₂O₃. The Krn + Tlc could be a more important assemblage in B-bearing whiteschists than has been reported to date, particularly at pressures where orthoamphibole is no longer stable. Received: 21 April 1997 / Accepted: 13 October 1997     

Open system alkaline magmatism in northern Kenya: evidence from U-series disequilibria and radiogenic isotopes

U-series activity ratios, Sr-Nd-Pb isotopic ratios and major and trace element compositions have been determined on young basalts (<10 ka) and trachytes from the volcano Emuruangogolak in the Kenya Rift Valley. The basalts are mildly alkaline and are associated with small volumes of hawaiite. The mafic rocks are characterised by high (²³⁰Th/²³²Th) (≥1.06) with low (²³⁸U/²³⁰Th) ratios (≤0.72). They have variable incompatible trace element ratios (e.g. Zr/Nb, Ba/Zr), indicating that they represent a number of magmatic lineages. The trachytes, which comprise both comenditic and pantelleritic varieties, have significantly lower (²³⁰Th/²³²Th) ratios than the basalts, with clear differences between pantelleritic and comenditic types. The (²³⁸U/²³⁰Th) ratios in the pantellerites range from less, to greater, than 1. The variations in composition and isotopic diversity must represent different sources for the trachytes. Internal isochrons for the trachytes give U-Th ages of 14 to 40 ka, similar to single crystal laser fusion ⁴⁰Ar/³⁹Ar ages from sanidine phenocrysts (16–38 ka) for the same rocks. Post-crystallisation residence times of the trachytes were very short, implying relatively rapid movement of trachyte from magma chamber to the surface. Variations in the initial (²³⁰Th/²³²Th)₀ ratios (0.69–1.14) of both basalts and trachytes indicate that Emuruangogolak has erupted a large range of isotopically diverse magmas over a very short period of time (38 ka), from conduits closely spaced around the summit of the volcano. Received: 29 May 1996 / Accepted: 24 November 1997