Oxidative dissolution potential of biogenic and abiogenic TcO2 in subsurface sediments

Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state and less mobile in the reduced form [Tc(IV)O₂·nH₂O]. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO₂-like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 μm-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass-transfer-limited migration of O₂ into intra-aggregate and intraparticle domains where Tc(IV) existed; and the formation of unique, oxidation-resistant, intragrain Tc(IV)-Fe(III) molecular species.     

Adsorption of Metal Ions onto the Chemically Modified Agricultural Waste

This paper discusses about the adsorption of metal ions such as Cu(II), Cd(II), Zn(II), and Ni(II) from aqueous solution by sulfuric acid treated cashew nut shell (STCNS). The adsorption process depends on the solution pH, adsorbent dose, contact time, initial metal ions concentration, and temperature. The adsorption kinetics was relatively fast and equilibrium was reached at 30 min. The adsorption equilibrium follows Langmuir adsorption isotherm model. The maximum adsorption capacity values of the modified cashew nut shell (CNS) for metal ions were 406.6 mg/g for Cu(II), 436.7 mg/g for Cd(II), 455.7 mg/g for Zn(II), and 456.3 mg/g for Ni(II). The thermodynamic study shows the adsorption of metal ions onto the STCNS was spontaneous and exothermic in nature. The kinetics of metal ions adsorption onto the STCNS followed a pseudo‐second‐order kinetic model. The external mass transfer controlled metal ions removal at the earlier stages and intraparticle diffusion at the later stages of adsorption. A Boyd kinetic plot confirms that the external mass transfer was the slowest step involved in the adsorption of metal ions onto the STCNS. A single‐stage batch adsorber was designed using the Langmuir adsorption isotherm equation.     

Mineralogical and Thermoluminescence Characterizations of the River Sediments from Tamilnadu, India

In this study, the mineralogical characterizations of the sediments have been carried out using Fourier Transform Infrared (FTIR) spectroscopic and XRD technique. The extinction co-efficient and crystallinity index are calculated to know the relative distribution of major minerals and crystalline nature of quartz, respectively. From the FTIR and XRD techniques, the minerals, such as quartz, microcline feldspar, orthoclase feldspar, kaolinite, calcite, gibbsite, montmorillonite, smectite, palygorskite, organic carbon, zircon, monazite, montmorillonite, and hornblende are identified. Thermoluminescence (TL) behavior of the sediments has been studied through the measurements of both Natural Thermoluminescence (NTL) and Artificial Thermoluminescence (ATL). Correlation analysis has been carried out among the parameters obtained from both mineral and TL analyses to know the existing interrelations. The obtained correlations are discussed, and it is suggested that the NTL and ATL measurements of the sediments show the valuable information about the sedimentation process. Thus, we conclude that the TL is the easiest tool to find out the sedimentation of the river.