Pertechnetate-Induced Addition of Sulfide in Small Olefinic Acids: Formation of [TcO(dimercaptosuccinate)2]5- and [TcO(mercaptosuccinate)2]3- Analogues.

Technetium-99 (99Tc) is important to the nuclear fuel cycle as a long-lived radionuclide produced in ∼6% fission yield from 235U or 239Pu. In its most common chemical form, namely, pertechnetate (99TcO4-), it is environmentally mobile. In situ hydrogen sulfide reduction of pertechnetate has been proposed as a potential method to immobilize environmental 99TcO4- that has entered the environment. Reactions of 99TcO4- with sulfide in solution result in the precipitation of Tc2S7 except when olefinic acids, specifically fumaric or maleic acid, are present; a water-soluble 99Tc species forms. NMR (1H, 13C, and 2D methods) and X-ray absorption spectroscopy [XAS; near-edge (XANES) and extended fine structure (EXAFS)] studies indicate that sulfide adds across the olefinic bond to generate mercaptosuccinic acid (H3MSA) and/or dimercaptosuccinic acid (H4DMSA), which then chelate(s) the 99Tc to form [99TcO(MSA)2]3-, [99TcO(DMSA)2]5-, or potentially [99TcO(MSA)(DMSA)]4-. 2D NMR methods allowed identification of the products by comparison to 99Tc and nonradioactive rhenium standards. The rhenium standards allowed further identification by electrospray ionization mass spectrometry. 99TcO4- is essential to the reaction because no sulfide addition occurs in its absence, as determined by NMR. Computational studies were performed to investigate the structures and stabilities of the potential products. Because olefinic acid is a component of the naturally occurring humic and fulvic acids found in soils and groundwater, the viability of in situ hydrogen sulfide reduction of environmental 99TcO4- as an immobilization method is evaluated.

Inferring the geometry of fourth-period metallic elements in arabidopsis thaliana seeds using synchrotron-based multi-angle X-ray fluorescence mapping.

BACKGROUND: Improving our knowledge of plant metal metabolism is facilitated by the use of analytical techniques to map the distribution of elements in tissues. One such technique is X-ray fluorescence (XRF), which has been used previously to map metal distribution in both two and three dimensions. One of the difficulties of mapping metal distribution in two dimensions is that it can be difficult to normalize for tissue thickness. When mapping metal distribution in three dimensions, the time required to collect the data can become a major constraint. In this article a compromise is suggested between two- and three-dimensional mapping using multi-angle XRF imaging. METHODS: A synchrotron-based XRF microprobe was used to map the distribution of K, Ca, Mn, Fe, Ni, Cu and Zn in whole Arabidopsis thaliana seeds. Relative concentrations of each element were determined by measuring fluorescence emitted from a 10 microm excitation beam at 13 keV. XRF spectra were collected from an array of points with 25 or 30 microm steps. Maps were recorded at 0 and 90 degrees , or at 0, 60 and 120 degrees for each seed. Using these data, circular or ellipsoidal cross-sections were modelled, and from these an apparent pathlength for the excitation beam was calculated to normalize the data. Elemental distribution was mapped in seeds from ecotype Columbia-4 plants, as well as the metal accumulation mutants manganese accumulator 1 (man1) and nicotianamine synthetase (nasx). CONCLUSIONS: Multi-angle XRF imaging will be useful for mapping elemental distribution in plant tissues. It offers a compromise between two- and three-dimensional XRF mapping, as far as collection times, image resolution and ease of visualization. It is also complementary to other metal-mapping techniques. Mn, Fe and Cu had tissue-specific accumulation patterns. Metal accumulation patterns were different between seeds of the Col-4, man1 and nasx genotypes.

Kinetics of uranium(VI) reduction by hydrogen sulfide in anoxic aqueous systems.

Aqueous U(VI) reduction by hydrogen sulfide was investigated by batch experiments and speciation modeling; product analysis by transmission electron microscopy (TEM) was also performed. The molar ratio of U(VI) reduced to sulfide consumed, and the TEM result suggested that the reaction stoichiometry could be best represented by UO2(2+) + HS- = UO2+ S* + H+. At pH 6.89 and total carbonate concentration ([CO32-]T) of 4.0 mM, the reaction took place according to the following kinetics: -d[U(VI)]/dt = 0.0103[U(VI)][S2-]T0.54 where [U(VI)] is the concentration of hexavalent uranium, and [S2-]T is the total concentration of sulfide. The kinetics of U(VI) reduction was found to be largely controlled by [CO32-]T (examined from 0.0 to 30.0 mM) and pH (examined from 6.37 to 9.06). The reduction was almost completely inhibited with the following [CO32-]T and pH combinations: [(> or = 15.0 mM, pH 6.89); (> or = 4.0 mM, pH 8.01); and (> or = 2.0 mM, pH 9.06)]. By comparing the experimental results with the calculated speciation of U(VI), it was found that there was a strong correlation between the measured initial reaction rates and the calculated total concentrations of uranium-hydroxyl species; we, therefore, concluded that uranium-hydroxyl species were the ones being reduced by sulfide, not the dominant U-carbonate species present in many carbonate-containing systems.