Aerosol removal coefficients based on 7Be, 210Pb,and 210Po radionuclides in the urban atmosphere

Journal of Atmospheric Chemistry - In this study, the aerosol removal coefficients based on 7Be, 210Pb and 210Po radionuclides in the urban air, in Lodz, Poland, were investigated over 3 years,...     

Modeling discrete gas bubble formation and mobilization during subsurface heating of contaminated zones

During thermal remediation the increase in subsurface temperature can lead to bubble formation and mobilization. In order to investigate the effect of gas formation on resulting aqueous concentrations, a 2D finite difference flow and mass transport model was developed which incorporates a macroscopic invasion percolation (MIP) model to simulate bubble expansion and movement. The model was used to simulate three soil scenarios with different permeabilities and entry pressures at various operating temperatures and groundwater velocities. It was observed that discrete bubble formation occurred in all three soils, upward mobility being limited by lower temperatures and higher entry pressures. Bubble mobilization resulted in a different aqueous mass distribution than if no discrete gas formation was modeled, especially at higher temperatures. This was a result of bubbles moving upwards to cooler areas, then collapsing, and contaminating previously clean zones. The cooling effect also led to possible non-aqueous phase liquid (NAPL) formation which was not predicted using a model without discrete bubble formation.     

Specific effects of background electrolytes on the kinetics of step propagation during calcite growth

The mechanisms by which background electrolytes modify the kinetics of non-equivalent step propagation during calcite growth were investigated using Atomic Force Microscopy (AFM), at constant driving force and solution stoichiometry. Our results suggest that the acute step spreading rate is controlled by kink-site nucleation and, ultimately, by the dehydration of surface sites, while the velocity of obtuse step advancement is mainly determined by hydration of calcium ions in solution. According to our results, kink nucleation at acute steps could be promoted by carbonate-assisted calcium attachment. The different sensitivity of obtuse and acute step propagation kinetics to cation and surface hydration could be the origin of the reversed geometries of calcite growth hillocks (i.e., rate of obtuse step spreading < rate of acute step spreading) observed in concentrated (ionic strength, IS = 0.1) KCl and CsCl solutions. At low IS (0.02), ion-specific effects seem to be mainly associated with changes in the solvation environment of calcium ions in solution. With increasing electrolyte concentration, the stabilization of surface water by weakly paired salts appears to become increasingly important in determining step spreading rate. At high ionic strength (IS = 0.1), overall calcite growth rates increased with increasing hydration of calcium in solution (i.e., decreasing ion pairing of background electrolytes for sodium-bearing salts) and with decreasing hydration of the carbonate surface site (i.e., increasing ion pairing for chloride-bearing salts). Changes in growth hillock morphology were observed in the presence of Li⁺, F⁻ and , and can be interpreted as the result of the stabilization of polar surfaces due to increased ion hydration. These results increase our ability to predict crystal reactivity in natural fluids which contain significant amounts of solutes.     

Application of organic petrology and geochemistry to coal waste studies

Coal wastes produced during mining activities are commonly deposited in nearby dumps. These wastes mostly composed of minerals and variable amounts (usually 20-30%) of organic matter start to weather immediately after deposition. Oxidation of the organic matter can lead to self heating and self combustion as a result of organic and mineral matter transformations. The degree of alteration depends on the properties of the wastes, i.e., the maceral and microlithotype composition of the organic matter and its rank.Alteration of wastes also depends on the heating history, i.e., the rate of heating, final heating temperature, duration of heating, and the degree of air access. Although air is probably necessary to initiate and drive the heating processes, these usually take place under relatively oxygen depleted conditions. With slow heating, color of organic matter particles changes, irregular cracks and oxidation rims develop around edges and cracks, and bitumen is expelled. As a result, massive and detritic isotropic and strongly altered organic matter forms. On the other hand, higher heating rates cause the formation of devolatilization pores, oxidation rims around these pores and along cracks, vitrinite-bands-mantling particles, and bitumen expulsions.Organic compounds generated from the wastes include n-alkanes, iso-alkanes, alkylcyclohexanes, acyclic isoprenoids, mainly pristane, phytane and, in some cases, farnesane, sesquiterpanes, tri- and tetracyclic diterpanes, tri- and pentacyclic triterpanes, and steranes, polycyclic aromatic hydrocarbons (mostly with two- to five rings, rarely six rings), and phenols. The compounds formed change during the heating history. The fact that phenols are found in dumps where heating has not yet been completed, but are absent in those where heating ceased previously suggests the presence of water washing. The organic compounds formed may migrate within the dumps. However, when they migrate out of the dumps, they become a hazard to environment.This paper is a review on transformations of organic matter (both maceral composition and reflectance and chemical composition) in coal wastes deposited in coal waste dumps. Immediately after deposition the wastes are exposed to weathering conditions and sometimes undergo self heating processes.     

The petrogenesis of granitoid rocks unusually rich in apatite in the Western Tatra Mts. (S-Poland, Western Carpathians)

In the bottom part of the tongue-shaped, layered granitoid intrusion, exposed in the Western Tatra Mts., apatite-rich granitic rocks occur as pseudo-layers and pockets between I-type hybrid mafic precursors and homogeneous S-type felsic granitoids. The apatite-rich rocks are peraluminous (ASI?=?1.12–1.61), with P₂O₅ contents ranging from 0.05 to 3.41 wt.% (<7.5 vol.% apatite), shoshonitic to high-K calc-alkaline. Apatite is present as long-prismatic zoned crystals (Ap₁) and as large xenomorphic unzoned crystals (Ap₂). Ap₁ apatite and biotite represent an early cumulate. Feldspar and Ap₂ textural relations may reflect the interaction of the crystal faces of both minerals and support a model based on local saturation of (P, Ca, F) versus (K, Na, Al, Si, Ba) in the border zones. Chondrite-normalized REE patterns for the apatite rocks and for pure apatite suggest apatite was a main REE carrier in these rocks. Minerals characteristics and the whole rock chemistry suggest both reduced S-type and I-type magma influenced the apatite-rich rocks. The field observations, mineral and rock chemistry as well as mass-balance calculations point out that the presence of apatite-rich rocks may be linked to the continuous mixing of felsic and mafic magmas, creating unique phosphorus- and aluminium-rich magma portions. Formation of these rocks was initially dominated by the complex flowage-controlled and to some extent also gravity-driven separation of early-formed zoned minerals and, subsequently, by local saturation in the border zones of growing feldspar and apatite crystals. Slow diffusion in the phosphorus-rich magma pockets favoured the local saturation and simultaneous crystallization of apatite and feldspars in a crystal-ladden melt.     

Impact of single inclined faults on the fluid flow and heat transport: results from 3-D finite element simulations

The impact of inclined faults on the hydrothermal field is assessed by adding simplified structural settings to synthetic models. This study is innovative in carrying out numerical simulations because it integrates the real 3-D nature of flow influenced by a fault in a porous medium, thereby providing a useful tool for complex geothermal modelling. The 3-D simulations for the coupled fluid flow and heat transport processes are based on the finite element method. In the model, one geological layer is dissected by a dipping fault. Sensitivity analyses are conducted to quantify the effects of the fault’s transmissivity on the fluid flow and thermal field. Different fault models are compared with a model where no fault is present to evaluate the effect of varying fault transmissivity. The results show that faults have a significant impact on the hydrothermal field. Varying either the fault zone width or the fault permeability will result in relevant differences in the pressure, velocity and temperature field. A linear relationship between fault zone width and fluid velocity is found, indicating that velocities increase with decreasing widths. The faults act as preferential pathways for advective heat transport in case of highly transmissive faults, whereas almost no fluid may be transported through poorly transmissive faults.     

Computing Lippmann Diagrams from Direct Calculation of Mixing Properties of Solid Solutions: Application to the Barite-Celestite System

The Lippmann diagram for the system(Ba, Sr)SO₄-H₂O was computed at 25 °Cby determining the solid-phase activity coefficientsfrom first principles calculations. Directcalculations of the mixing properties of thebarite-celestite series indicate this solid solutionbehaves as non-ideal and non-regular. At 25 °C,the enthalpy of mixing shows a minimum around 50 mole% SrSO₄ due to an ordering tendency. Thefree energy of mixing shows two minima that delimit awide and symmetric miscibility gap (from 2.1 to 97.9 mole% SrSO₄) at this temperature. The excessfree energy of mixing requires a Guggenheim expansionseries of 5 terms to be described, where the termswith odd exponents are null as a consequence of thesymmetric distribution of the mixing properties withcomposition. The Lippmann diagram shows a peritecticpoint that corresponds to the composition of an aqueoussolution which is simultaneously at equilibrium withthe two extremes of the miscibility gap. The largedifference between the solubility products of theendmembers involves a strong preferential partitioningof the less soluble endmember towards the solid phase,which explains the extremely Ba-poor composition ofthe aqueous solution (aqueous activity fraction forBa²⁺ = 0.000446 ) at the peritectic point.     

An Atomic Force Microscopy study of the growth of calcite in the presence of sodium sulfate

In situ atomic force microscopy (AFM) has been used to compare the growth of pure calcite and the growth of calcite in the presence of sulfate ions from aqueous solutions at a constant value of supersaturation (S.I. = 0.89) with respect to calcite. The effect of sulfate ions on calcite growth rates is determined and a potential incorporation of sulfate ions is identified in the calcite during growth. Solutions supersaturated with respect to calcite with solution concentration ratio of one and a constant pH of 10.2, were prepared and sulfate was added as Na₂SO₄ aqueous solution. The solution composition was readjusted in order to keep the supersaturation and pH constant. PHREEQC was used to determine relevant solution concentrations. In situ AFM experiments of calcite growth were performed using a fluid cell and flowing solutions passed over a freshly cleaved calcite surface. Growth rates were determined from the closure of the rhombohedral etch pits induced by initial dissolution with pure water. The spreading rate of 2-dimensional nuclei was also measured. At low concentrations of sulfate (≤ 0.5 mM), no effect on the growth rate of the calcite was observed. At higher concentrations (2 to 3 mM) of sulfate, the growth rate increased, possibly because a higher concentration of calcium and carbonate was necessary to maintain the supersaturation constant. At much higher concentrations of additional sulfate (up to 60 mM) the growth rate of the calcite was substantially decreased, despite the fact that a further increase of calcium and carbonate was required. The morphology of 2-dimensional growth nuclei became increasingly elongated with increasing sulfate content. Measurements of step height showed that newly grown steps were approximately 1 Å higher when grown in high sulfate concentrations, compared to steps grown in sulfate-free solutions. At sulfate concentrations above 5 mM the growth mechanism changes from layer growth to surface roughening. These observations suggest that the new growth has incorporated sulfate into the calcite surface.