Assessment of Management Oxides for the Sorption of Radionuclides

Recent research has shown that certain manganese oxides have the ability to sorb aqueous metal cations much more efficiently than any of the naturally occurring iron oxides when normalized to surface area. This ability is, at least in part, related to the internal sites available in many manganese oxide structures, including those within tunnels and between sheets. Additionally, a new naturally-occurring manganese oxide structurally related to vernadite ({delta}-MnO{sub 2}), collected along the Clark Fork River in western Montana, USA, has shown the ability to sorb arsenate, an anionic complex. The potential for manganese oxides to sorb anions has made it an attractive material as a radionuclide ''getter''. According to the US Department of Energy's Total Systems Performance Assessment, technetium and iodine are two major anionic radionuclides contributing to the list of potential contaminants released from Yucca Mountain repository, Nevada, USA. These two radionuclides are extremely problematic because they are very mobile in the environment. This project involves running flow-through sorption experiments using rhenium (a surrogate for technetium) and stable iodine as sorbates and several synthetic manganese oxides, including birnessite, vernadite, cryptomelane, and possibly the new vernadite-like phase mentioned earlier, as sorbants. For all synthesis reactions, manganese (VII) salts are reduced to manganese (III,IV) oxides. The different oxides are produced from specific reductants and/or the addition of heat, followed by multiple washing steps. To verify that the proper phases have been synthesized, all oxides are analyzed using transmission electron microscopy (TEM) and powder X-ray diffraction (XRD). The sorption experiments will be run in flow-through reactors bearing the aqueous complex of interest, where solutions, at various temperatures, pH's, and ionic strengths, will pass through a bed of one of the manganese oxides. The effluent solution will be analyzed using aqueous spectroscopic methods and the reacted solids will be analyzed using microscopy (field emission scanning electron microscopy, FE-SEM; and TEM), structure analysis (XRD), bulk chemical spectroscopy (energy dispersive spectroscopy, EDS), and surface sensitive spectroscopy (X-ray photoelectron spectroscopy, XPS)

Using Macro- and Microscale Preservation in Vertebrate Fossils as Predictors for Molecular Preservation in Fluvial Environments

Exceptionally preserved fossils retain soft tissues and often the biomolecules that were present in an animal during its life. The majority of terrestrial vertebrate fossils are not traditionally considered exceptionally preserved, with fossils falling on a spectrum ranging from very well-preserved to poorly preserved when considering completeness, morphology and the presence of microstructures. Within this variability of anatomical preservation, high-quality macro-scale preservation (e.g., articulated skeletons) may not be reflected in molecular-scale preservation (i.e., biomolecules). Excavation of the Hayden Quarry (HQ; Chinle Formation, Ghost Ranch, NM, USA) has resulted in the recovery of thousands of fossilized vertebrate specimens. This has contributed greatly to our knowledge of early dinosaur evolution and paleoenvironmental conditions during the Late Triassic Period (~212 Ma). The number of specimens, completeness of skeletons and fidelity of osteohistological microstructures preserved in the bone all demonstrate the remarkable quality of the fossils preserved at this locality. Because the Hayden Quarry is an excellent example of good preservation in a fluvial environment, we have tested different fossil types (i.e., bone, tooth, coprolite) to examine the molecular preservation and overall taphonomy of the HQ to determine how different scales of preservation vary within a single locality. We used multiple high-resolution mass spectrometry techniques (TOF-SIMS, GC-MS, FT-ICR MS) to compare the fossils to unaltered bone from extant vertebrates, experimentally matured bone, and younger dinosaurian skeletal material from other fluvial environments. FT-ICR MS provides detailed molecular information about complex mixtures, and TOF-SIMS has high elemental spatial sensitivity. Using these techniques, we did not find convincing evidence of a molecular signal that can be confidently interpreted as endogenous, indicating that very good macro- and microscale preservation are not necessarily good predictors of molecular preservation. © 2022 by the authors.Open access journalThis item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Water-dispersible nanocolloids and higher temperatures promote the release of carbon from riparian soil

Increasing temperatures in alpine regions accompanied by glacial retreat is occurring rapidly due to climate change. This may affect riparian soils by increasing weathering rates, resulting in greater organic carbon (OC) release to rivers via movement of iron-containing colloids and nanominerals. Increased concentrations of iron- or silcate-nanominerals would result in higher surface area for OC adsorption. To test the influence of temperature on OC leaching, we examined mineral weathering and nanocolloid facilitated release of OC through a series of controlled laboratory batch and column experiments using sediment from the banks of the Nisqually River, Mount Rainier in Washington State (USA). Additional experiments were conducted using the same sediments, but with an illite amendment added to test the influence of additional surface area and nanominerals that many sediments along the Nisqually River contain. These higher- and lower-surface-area sediments (i.e., sediments with and without the illite amendment) were incubated for 90 d at 4 or 20 degrees C, followed by batch and column OC leaching tests. Results show that OC leaching rates for 20 degrees C were two to three times greater than for 4 degrees C. Further, our results suggest that nanocolloids are responsible for moving this increased OC load from these sediments. When hydrologically connected, OC is released from bank sediments to rivers faster than presently anticipated in fluvial environments experiencing climate change-induced glacial retreat. Further, a one-dimensional, finite-element computational model developed for this study estimates that a 1 degrees C increase in temperature over a 90-d summer runoff period increases the OC release rate from sediments by 79%.11Ysciescopu

Transformation of femtoliter metal cups to oxide cups: Chemical mapping by scanning Auger spectroscopy

Cup-like structures of In, Sn and Nb on Si substrates with femtoliter capacity obtained by pulsed laser ablation, have been subjected to different oxidation treatments and examined employing spatially resolved scanning Auger spectroscopy and microscopy (SR-AES and SAM). The as-prepared cups, when exposed to ambient are found to have a native oxide layer on the surface that could be easily removed by Ar ion sputtering to result in clean metal cups, suitable for functionalization. In the case of In cups, the thin metal layer at the bottom of the cups could be removed easily by sputtering to form In rings. The cups subjected to external oxidation have a thicker oxide layer in comparison to in-situ dosing of oxygen. In the case of Nb cups, the high temperature treatment employed during oxidation resulted in segregation of Si to the surface of the cup. There is also evidence for the formation of metal-silicon alloy at the center of the cups, especially of Sn and Nb, during the oxidation treatment at elevated temperatures