Speciation of Uranium in Sediments before and after In situ Biostimulation

The success of sequestration-based remediation strategies will depend on detailed information, including the predominant U species present as sources before biostimulation and the products produced during and after in situ biostimulation. We used X-ray absorption spectroscopy to determine the valence state and chemical speciation of U in sediment samples collected at a variety of depths through the contaminant plume at the Field Research Center at Oak Ridge, TN, before and after approximately 400 days of in situ biostimulation, as well as in duplicate bioreduced sediments after 363 days of resting conditions. The results indicate that U(VI) in subsurface sediments was partially reduced to 10–40% U(IV) during biostimulation. After biostimulation, U was no longer bound to carbon ligands and was adsorbed to Fe/Mn minerals. Reduction of U(VI) to U(IV) continued in sediment samples stored under anaerobic condition at <4 °C for 12 months, with the fraction of U(IV) in sediments more than doubling and U concentrations in the aqueous phase decreasing from 0.5-0.74 to <0.1 µM. A shift of uranyl species from uranyl bound to phosphorus ligands to uranyl bound to carbon ligands and the formation of nanoparticulate uraninite occurred in the sediment samples during storage.

Self-potential signatures associated with an injection experiment at an in situ biological permeable reactive barrier

Strategies available to evaluate the performance of in situ permeable reactive barriers are currently not well developed and often rely on fluid and media sampling directly from the permeable reactive barrier (PRB). Here, we investigate the utility of the self-potential (SP) method as a technique to monitor in situ PRB performance. Our field study was conducted at in situ biological PRB in Portadown, Northern Ireland, UK, which was emplaced to assist in the remediation of groundwater contamination (e.g., hydrocarbons, ammonia) that resulted from the operations and waste disposal practices of a former gasworks. Borehole SP measurements were collected during the injection of contaminant groundwater slugs in an attempt to monitor/detect the response of the microbial activity associated with the breakdown of the added contaminants into the PRB. In addition, an uncontaminated groundwater slug was injected into a different portion of the PRB as a ‘control’ and SP measurements were collected for comparison to the SP response of the contaminant slugs. The results of the SP signals due to the contaminant injections show that the magnitude of the response was relatively small (<10 mV) yet showed a consistent decrease during both contaminant injections. The net decrease in SP recorded during the contaminant injections slowly rebounded to near background values through ~44 hours post-injection. The SP response during the uncontaminated injection showed a slight, albeit negligible (within the margin of error), 1 mV increase in the measured SP signals, in contrast to the contaminant injections. The results of the SP signals recorded from the uncontaminated groundwater injection also persisted through a period of ~47 hours after injection but show a net increase in SP relative to pre-injection values. Based on the difference in SP response between the contaminated and uncontaminated injections, we suggest that the responses are likely to be the result of differences in the chemistry of the injection types (contaminated versus uncontaminated) and in situ groundwater. We argue that the SP signals associated with the contaminated injections are dominated by diffusion (electrochemical) potential, possibly enhanced by a microbial effect. While the results of our investigation show a consistent SP response associated with the contaminant injections that is dominated by diffusional effects, further studies are required in order to better understand the effect of microbial activity on SP signals and the potential utility for the SP method to detect/monitor changes that may be indicative of biological PRB performance.

Studies of Microthrix parvicella in situ and in laboratory culture: production and use of specific antibodies

Physiological studies on M. parvicella have been conducted to determine the rate of growth of this organism in pure culture. The organism displayed a doubling time of 128 days despite its profuse abundance in a local Wastewater Treatment Plant (WWTW). An extensive survey has been ongoing since February 2000 into the extent of M. parvicella in the WWTW. A suite of monoclonal and polyclonal antibodies has been developed to detect and quantify M. parvicella.

DFT and in situ EXAFS investigation of gold/ceria-zirconia low-temperature water gas shift catalysts: Identification of the nature of the active form of gold

A combined experimental and theoretical investigation of the nature of the active form of gold in oxide-supported gold catalysts for the water gas shift reaction has been performed. In situ extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) experiments have shown that in the fresh catalysts the gold is in the form of highly dispersed gold ions. However, under water gas shift reaction conditions, even at temperatures as low as 100 degrees C, the evidence from EXAFS and XANES is only 14 consistent with rapid, and essentially complete, reduction of the gold to form metallic clusters containing about 50 atoms. The presence of Au-Ce distances in the EXAFS spectra, and the fact that about 15% of the gold atoms can be reoxidized after exposure to air at 150 degrees C, is indicative of a close interaction between a fraction (ca. 15%) of the gold atoms and the oxide support. Density functional theory (DFT) calculations are entirely consistent with this model and suggest that an important aspect of the active and stable form of gold under water gas shift reaction conditions is the location of a partially oxidized gold (Audelta+) species at a cerium cation vacancy in the surface of the oxide support. It is found that even with a low loading gold catalysts (0.2%) the fraction of ionic gold under water gas shift conditions is below the limit of detection by XANES (<5%). It is concluded that under water gas shift reaction conditions the active form of gold comprises small metallic gold clusters in intimate contact with the oxide support.

Dynamic in situ optical and magneto-optical monitoring of the growth of Co-Pd multilayers

In situ ellipsometry and Kerr polarimetry have been used to follow the continuous evolution of the optical and magneto- optical properties of multiple layers of Co and Pd during their growth. Films were sputter deposited onto a Pd buffer layer on glass substrates up to a maximum of N = 10 bi-layer periods according to the scheme glass/Pd(10)Ar x (0.3Co/3Pd) (nm). Magnetic hysteresis measurements taken during the deposition consistently showed strong perpendicular anisotropy at all stages of film growth following the deposition of a single monolayer of Co. Magneto-optic signals associated with the normal-incidence polar Kerr effect indicated strong polarization of Pd atoms at both Co-Pd and Pd-Co interfaces and that the magnitude of the complex magneto-optic Voigt parameter and the magnetic moment of the Pd decrease exponentially with distance from the interface with a decay constant of 1.1 nm(- 1). Theoretical simulations have provided an understanding of the observations and allow the determination of the ultrathin- film values of the elements of the skew-symmetric permittivity tensor that describe the optical and magneto-optical properties for both CO and Pd. Detailed structure in the observed Kerr ellipticity shows distinct Pd-thickness-dependent oscillations with a spatial period of about 1.6 nm that are believed to be associated with quantum well levels in the growing Pd layer.

Dynamic, in situ optical, magnetic and magneto-optical monitoring of the growth of Co/Au and Pd/Co/Au multilayer systems

The growth of magnetron sputtered Co/Au and Pd/Co/Au superlattices on Au and Pd buffer layers, deposited onto glass substrates, has been monitored optically and magneto-optically in real time, using rotating analyser ellipsometry and Kerr polarimetry, at a wavelength of 633 nm. The magneto-optical traces, combined with ex situ and in situ hysteresis loops, provide a detailed and informative fingerprint of the optical and magnetic properties of the films as they evolve during growth. For Co/Au, oscillations in the polar magneto-optical effect developed during the deposition of An overlayers on Co and these may be attributed to quantum well states. However, the hysteresis measurements show that the magnetic field required to maintain saturation magnetization throughout the experiment was larger than available in situ, introducing a degree of confusion concerning the interpretation of the data. This problem was overcome by the incorporation of Pd layers into the Co/Au structure, thereby eliminating variation in magnetic orientation during growth of the Au layers as a contributory factor to the observations.