Electron-impact excitation of Fe II

We report in this paper the computation of accurate total collision strengths and effective collision strengths for electron-impact excitation of FeII, using the parallel R-matrix program PRMAT. Target states corresponding to the 3d(6)4s, 3d(7), 3d(6)4p and 3d(5)4s4s basis configurations were included in the calculations giving rise to a 113 LS state 354 coupled channel problem. Following a detailed systematic study of correlation effects in both the target state and collision wavefunctions, it was found that an additional 21 configuration functions needed to be included in the Configuration Interaction expansion to obtain significantly more accurate target states and collision wavefunctions. This much improved 26-configuration model has been used to calculate converged total effective collision strengths for all sextet to quartet transitions among these levels with total spin S=2, giving a total of 1785 lines. These calculations have laid the foundation for an approach which may be adopted in the study of electron collisions with the low ionization stages of other iron peak elements. The work has been further extended with the commencement of a Breit-Pauli relativistic calculation for one of the smaller models and includes 262 fine-structure levels and over 1800 coupled channels. At the same time the PRMAT parallel R-matrix package is being extended to include relativistic effects which will allow us to attempt the more sophisticated 26-configuration model and produce for the first time the amount and quality of atomic data required to perform a meaningful synthesis of the Fe II spectrum.

Localized Flux Maxima of Arsenic, Lead, and Iron around Root Apices in Flooded Lowland Rice

In wetland-adapted plants, such as rice, it is typically root apexes, sites of rapid entry for water/nutrients, where radial oxygen losses (ROLs) are highest. Nutrient/toxic metal uptake therefore largely occurs through oxidized zones and pH microgradients. However, the processes controlling the acquisition of trace elements in rice have been difficult to explore experimentally because of a lack of techniques for simultaneously measuring labile trace elements and O2/pH. Here, we use new diffusive gradients in thin films (DGT)/planar optode sandwich sensors deployed in situ on rice roots to demonstrate a new geochemical niche of greatly enhanced As, Pb, and Fe(II) mobilization into solution immediately adjacent to the root tips characterized by O2 enrichment and low pH. Fe(II) mobilization was congruent to that of the peripheral edge of the aerobic root zone, demonstrating that the Fe(II) mobilization maximum only developed in a narrow O2 range as the oxidation front penetrates the reducing soil. The Fe flux to the DGT resin at the root apexes was 3-fold higher than the anaerobic bulk soil and 27 times greater than the aerobic rooting zone. These results provide new evidence for the importance of coupled diffusion and oxidation of Fe in modulating trace metal solubilization, dispersion, and plant uptake.

Mineralogical Characteristics and Transformations during Long-Term Operation of a Zerovalent Iron Reactive Barrier

Design and operation of Fe⁰ permeable reactive barriers (PRBs) can be improved by understanding the long-term mineralogical transformations that occur within PRBs. Changes in mineral precipitates, cementation, and corrosion of Fe⁰ filings within an in situ pilot-scale PRB were examined after the first 30 months of operation and compared with results of a previous study of the PRB conducted 15 months earlier using X-ray diffraction and scanning electron microscopy employing energy dispersive X-ray and backscatter electron analyses. Iron (oxy)hydroxides, aragonite, and maghemite and/or magnetite occurred throughout the cores collected 30 mo after installation. Goethite, lepidocrocite, mackinawite, aragonite, calcite, and siderite were associated with oxidized and cemented areas, while green rusts were detected in more reduced zones. Basic differences from our last detailed investigation include (i) mackinawite crystallized from amorphous FeS, (ii) aragonite transformed into calcite, (iii) akaganeite transformed to goethite and lepidocrocite, (iv) iron (oxy)hydroxides and calcium and iron carbonate minerals increased, (v) cementation was greater in the more recent study, and (vi) oxidation, corrosion, and disintegration of Fe⁰ filings were greater, especially in cemented areas, in the more recent study. If the degree of corrosion and cementation that was observed from 15 to 30 mo after installation continues, certain portions of the PRB (i.e., up-gradient entrance of the ground water to the Fe⁰ section of the PRB) may last less than five more years, thus reducing the effectiveness of the PRB to mitigate contaminants.

Impact of sample preparation on mineralogical analysis of zero-valent iron reactive barrier materials

Permeable reactive barriers (PRBs) of zero-valent iron (Fe⁰) are increasingly being used to remediate contaminated ground water. Corrosion of Fe⁰ filings and tbe formation of precipitates can occur when the PRB material comes in contact with ground water and may reduce the lifespan and effectiveness of the barrier. At present, there are no routine procedures for preparing and analyzing the mineral precipitates from Fe⁰ PRB material. These procedures are needed because mineralogical composition of corrosion products used to interpret the barrier processes can change with iron oxidation and sample preparation. The objectives of this study were (i) to investigate a method of preparing Fe⁰ reactive barrier material for mineralogical analysis by X-ray diffraction (XRD), and (ii) to identify Fe mineral phases and rates of transformations induced by different mineralogical preparation techniques. Materials from an in situ Fe⁰ PRB were collected by undisturbed coring and processed for XRD analysis after different times since sampling for three size fractions and by various drying treatments. We found that whole-sample preparation for analysis was necessary because mineral precipitates occurred within the PRB material in different size fractions of the samples. Green rusts quickly disappeared from acetone-dried samples and were not present in air-dried and oven-dried samples Maghemite/magnetite content increased over time and in oven-dried samples, especially after heating to 105°C. We conclude that care must be taken during sample preparation of Fe⁰ PRB material, especially for detection of green rusts, to ensure accurate identification of minerals present within the barrier system.

Density Functional Theory Study of Iron and Cobalt Carbides for Fischer-Tropsch Synthesis

Carbides are important phases in heterogeneous catalysis. However, the understanding of carbide phases is inadequate: Fe and Co are the two commercial catalysts for Fischer-Tropsch (FT) synthesis, and experimental work showed that Fe carbide is the active phase in FT synthesis, whereas the appearance of Co carbide is considered as a possible deactivation cause, TO understand very different catalytic roles of carbides, all the key elementary steps in FT synthesis, that is, CO dissociation, C(1) hydrogenation, and C(1)+C(1) coupling, are extensively investigated on both carbide surfaces using first principles calculations. In particular, the most important issues in FT synthesis, the activity and methane selectivity, on the carbide surfaces are quantitatively determined and analyzed. They are also discussed together with metallic Fe and Co surfaces. It is found that (i) Fe carbide is more active than metallic Fe and has similar methane selectivity to Fe, being consistent with the experiments; and (ii) Co carbide is less active than Co and has higher methane selectivity, providing evidence on the molecular level to support the suggestion that the formation of Co carbide is a cause of relatively high methane selectivity and deactivation on Co catalysts.