Deposition of uranium precipitates in dolomitic gravel fill.

Uranium-containing precipitates have been observed in a dolomitic gravel fill near the Department of Energy (DOE) S-3 Ponds former waste disposal site as a result of exposure to acidic (pH 3.4) groundwater contaminated with U (33 mg L(-1)), Al3+ (900 mg L(-1)), and NO3- (14 000 mg L(-1)). The U containing precipitates fluoresce a bright green under ultraviolet (UV) short-wave light which identify U-rich coatings on the gravel. Scanning electron microscopy (SEM) microprobe analysis show U concentration ranges from 1.6-19.8% (average of 7%) within the coatings with higher concentrations at the interface of the dolomite fragments. X-ray absorption near edge structure spectroscopy (XANES) indicate that the U is hexavalent and extended X-ray absorption fine structure spectroscopy (EXAFS) shows that the uranyl is coordinated by carbonate. The exact nature of the uranyl carbonates are difficult to determine, but some are best described by a split K(+)-like shell similar to grimselite [K4Na(UO2)(CO3)3 x H2O] and other regions are better described by a single Ca(2+)-like shell similar to liebigite [Ca2(UO2)(CO3)3 x 11(H2O)] or andersonite [Na2CaUO2(CO3)3 x 6H2O]. The U precipitates are found in the form of white to light yellow cracked-formations as coatings on the dolomite gravel and as detached individual precipitates, and are associated with amorphous basalumnite [Al4(SO4)(OH)10 x 4H2O].

Hard X-ray micro(spectro)scopy: a powerful tool for the geomicrobiologists.

During the past few decades, the use of electron microscopy approaches - many developed by Terry Beveridge - to probe the physiology of microorganisms has become a mainstay in fields including microbiology, human health, and geomicrobiology. Recent developments of third-generation synchrotron X-ray sources and X-ray-based microscopy approaches for studying microbial systems have proved their utility as complements to the very powerful approaches regularly employed by electron microscopists. In addition, in recent geomicrobiological studies, researchers have begun to take advantage of the strengths of each technique by using the superior spatial resolution of the electron microscope (relative to the X-ray microscope) and the superior elemental sensitivity of the X-ray microscope (relative to the electron microscope), along with the ability of the X-ray microscope to spatially probe the chemical speciation of elements. The benefits of integrating these two nanoprobes for investigating the same microenvironments within a geomicrobial system are far superior to those of independent studies separately employing each probe.

Mixed-valence cytoplasmic iron granules are linked to anaerobic respiration.

Intracellular granules containing ferric and ferrous iron formed in Shewanella putrefaciens CN32 during dissimilatory reduction of solid-phase ferric iron. It is the first in situ detection at high resolution (150 nm) of a mixed-valence metal particle residing within a prokaryotic cell. The relationship of the internal particles to Fe(III) reduction may indicate a respiratory role.

X-ray absorption fine structure spectroscopy determination of the binding mechanism of tetrahedral anions to self assembled monolayers on mesoporous support.

X-ray absorption fine structure (XAFS) spectroscopy is used to investigate the chemical interaction between the end member [Cu(NH2)6] of self-assembled monolayers on mesoporous supports (SAMMS) and the tetrahedral anion SO4. The local structure about Cu indicates monodentate bonding between the SO4 anion and the SAMMS.

XAFS determination of the bacterial cell wall functional groups responsible for complexation of Cd and U as a function of pH.

Bacteria, which are ubiquitous in near-surface geologic systems, can affect the distribution and fate of metals in these systems through adsorption reactions between the metals and bacterial cell walls. Recently, Fein et al. (1997) developed a chemical equilibrium approach to quantify metal adsorption onto cell walls, treating the sorption as a surface complexation phenomenon. However, such models are based on circumstantial bulk adsorption evidence only, and the nature and mechanism of metal binding to cell walls for each metal system have not been determined spectroscopically. The results of XAFS measurements at the Cd K-edge and U L3-edge on Bacillus subtilis exposed to these elements show that, at low pH, U binds to phosphoryl groups while Cd binds to carboxyl functional groups.

XAS investigations of Fe(VI).

Recent attention has been given to a reexamination of results from the early Viking missions to Mars that suggested the presence of one or more strong oxidants in Martian soil. Since Fe is one of the main constituents of the Martian surface and Fe(VI) is known to be a highly reactive, strong oxidant, we have made XANES and EXAFS measurements of Fe(II), Fe(III), Fe(IV), and Fe(VI) in solid and solution forms. Results from these studies indicate a preedge XANES feature from Fe(VI) samples similar to that commonly seen from Cr(VI) samples. Results of first shell analysis indicate a linear relationship between the Fe-O bondlength and Fe valence state.

Biomass byproducts for the remediation of wastewaters contaminated with toxic metals.

Pollution of the environment with toxic metals is widespread and often involves large volumes of wastewater. Remediation strategies must be designed to support high throughput while keeping costs to a minimum. Biosorption is presented as an alternative to traditional physicochemical means for removing toxic metals from wastewater. We have investigated the metal binding qualities of two biomass byproducts that are commercially available in quantity and at low cost, namely "spillage", a dried yeast and plant mixture from the production of ethanol from corn, and ground corn cobs used in animal feeds. The biomass materials effectively removed toxic metals, such as Cu, Cs, Mo, Ni, Pb, and Zn, even in the presence of competing metals likely to be found in sulfide mine tailing ponds. The effectiveness of these biosorbents was demonstrated using samples from the Berkeley Pit in Montana. Investigations included column chromatography and slurry systems, and linear distribution coefficients are presented. X-ray spectroscopy was used to identify the binding sites for metals adsorbed to the spillage material. The results of our experiments demonstrate that the biosorption of metals from wastewaters using biomass byproducts is a viable and cost-effective technology that should be included in process evaluations.

Formation of sphalerite (ZnS) deposits in natural biofilms of sulfate-reducing bacteria.

Abundant, micrometer-scale, spherical aggregates of 2- to 5-nanometer-diameter sphalerite (ZnS) particles formed within natural biofilms dominated by relatively aerotolerant sulfate-reducing bacteria of the family Desulfobacteriaceae. The biofilm zinc concentration is about 10(6) times that of associated groundwater (0.09 to 1.1 parts per million zinc). Sphalerite also concentrates arsenic (0.01 weight %) and selenium (0.004 weight %). The almost monomineralic product results from buffering of sulfide concentrations at low values by sphalerite precipitation. These results show how microbes control metal concentrations in groundwater- and wetland-based remediation systems and suggest biological routes for formation of some low-temperature ZnS deposits.

X-ray imaging and microspectroscopy of plants and fungi.

X-ray fluorescence microscopy and microspectroscopy with micrometre spatial resolution and unprecedented capabilities for the study of biological and environmental samples are reported. These new capabilities are a result of both the combination of high-brilliance synchrotron radiation and high-performance X-ray microfocusing optics and the intrinsic advantages of X-rays for elemental mapping and chemical-state imaging. In this paper, these capabilities are illustrated by experimental results on hard X-ray phase-contrast imaging, X-ray fluorescence (XRF) imaging and microspectroscopy of mycorrhizal plant roots and fungi in their natural hydrated state. The XRF microprobe is demonstrated by the simultaneous mapping of the elemental distributions of P, S, K, Ca, Mn, Fe, Ni, Cu and Zn with a spatial resolution of approximately 1 x 3 micron and with an elemental sensitivity of approximately 500 p.p.b. Microspectroscopy with the same spatial resolution is demonstrated by recording near-edge X-ray absorption (XANES) spectra of Mn at a concentration of approximately 3 p.p.m.