Kinetics of the Formation and Dissolution of Ni Precipitates in a Gibbsite/Amorphous Silica Mixture

There have been a number of studies that have examined metal precipitation reactions on an array of natural soil materials. While many of these investigations have focused on model single-component systems, recent research has appeared on metal precipitation on soils and clay fractions of soils. However, few studies have explored mixed model component systems, which may lead to a better understanding of metal reactions on soils and clay fractions. Furthermore, only a few studies have appeared on the stability of the metal surface precipitates. In light of this, we investigated Ni sorption and dissolution kinetics and mechanisms on a mixture of gibbsite and amorphous silica by combining macroscopic studies with X-ray absorption fine structure (XAFS) and diffuse reflectance spectroscopies (DRS), and high-resolution thermogravimetric analysis (HRTGA). Batch sorption experiments were conducted at pH 7.5 and at different reaction times to elucidate the sorption process and to study the role of residence time on metal precipitate stability. Spectroscopic and HRTGA investigations revealed alpha-Ni(OH)(2) precipitates formed on the gibbsite/silica mixture initially and over time evolved to a Ni phyllosilicate. The available Si source was derived from partial dissolution of the sorbent during Ni sorption. With increasing residence time, the precipitate phases drastically increased in stability, as shown by decreasing amounts of Ni release as effected by nitric acid (HNO(3)) and ethylenediaminetetraacetic acid (EDTA) treatments. This aging effect may be explained by the silicate-for-nitrate exchange during the first days of reaction and subsequently by silicate polymerization and partial grafting onto the hydroxide layers to form a phyllosilicate precursor phase (R. G. Ford, A. C. Scheinost, K. G. Scheckel, and D. L. Sparks, Environ. Sci. Technol. 33(18), 3140-3144, 1999). Copyright 2000 Academic Press.     

Treatment of zinc-contaminated water using a multistage ferrihydrite sorption system

Previous studies demonstrated the environmental and economic benefits of treating lead(II)-contaminated water streams with ferrihydrite in multiple equilibrium sorption stages. In this work, multistage ferrihydrite sorption systems were evaluated for their effectiveness in reducing single-solute zinc(II) (Zn(II)) concentrations in contaminated water streams to very low levels. As for lead(II) (Pb(II)), experimental data and modeling results indicate that a multistage sorption system can significantly reduce Zn(II) effluent concentrations for the same total amount of sorbent or, alternatively, dramatically lower total sorbent consumption for the same effluent Zn(II) concentration. Compared to Pb(II), however, Zn(II) removal requires on the order of 10 times more sorbent to achieve the same target effluent concentration for the same pH and number of stages. Model predictions were made using a steady-state, multistage, equilibrium adsorber model that was previously developed for and integrated into OLI Systems' Environmental Simulation Program (ESP). The modified triple-layer model was used to simulate Zn(II) surface-liquid equilibria within the adsorber model. Engineering screening evaluations again indicate that a 2- to 3-stage sorption process can provide significant economic savings when compared to a 1-stage process operating with the same target effluent Zn(II) concentration. Additional equilibrium stages beyond 2 or 3 provide diminishing economic returns. The major economic driver for multiple contacting stages is reduced capital investment and operating costs for sludge handling, dewatering, and disposal.     

A new method for gaining insight into the chemistry of drying mineral surfaces using ATR-FTIR

Although it is understood that the chemical environment at a drying surface is likely to be quite different from that at a fully hydrated surface, the difficulty of quantitative measurement has meant that this potentially crucial aspect of surface chemistry has gone largely overlooked. As a result, most of our understanding comes from measurement before and after drying, with a gray region of speculation in between. An interesting natural example is the paradoxical reduction of Mn oxides in moist soils as they dry, because drying is usually considered an oxidative process. This phenomenon indicates that important chemical changes are occurring during drying and an approach is needed to probe the chemistry of drying surfaces. Here we show the suitability of attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy for real-time, in situ investigation of the drying solid-water interface, using the change in surface pH as an example. This was achieved by adsorbing thymol blue pH indicator (pK(a)=1.65) onto a natural Mn-rich clay and observing the real-time pH change, which dropped from pH 5 to below pH 1.65 with the removal of free water from the surface.     

Type 2 intramolecular nitroso Diels-Alder reaction. Synthesis and structure of bridgehead oxazinolactams

[reaction--see text] The type 2 intramolecular Diels-Alder cycloaddition utilizing N-acylnitroso dienophiles provides an efficient entry into bridged oxazinolactams. In contrast to the bimolecular counterpart, the reaction is completely regioselective. Structural characterization of the cycloadducts allows for evaluation of the olefin distortion and the degree of pyramidalization of the bridgehead oxazinolactam.     

Type 2 intramolecular N-acylnitroso Diels-Alder reaction: scope and application to the synthesis of medium ring lactams

Heteroatom variants of the type 2 intramolecular Diels-Alder reaction provide an efficient method for the preparation of bridged bicyclic heterocycles. The type 2 variant of the intramolecular N-acylnitroso Diels-Alder reaction is an effective method for the synthesis of bridged bicyclic oxazinolactams. Structural studies of the cycloadducts have allowed for quantification of the deformations of the bridgehead functionalities and provided a strategy for the stereoselective synthesis of substituted seven- and eight-membered ring lactams. Diastereoselective cycloadditions followed by cleavage of the oxazine ring afford azepin-2-ones or azocin-2-ones.