Gender bias in teaching evaluations: the causal role of department gender composition.

Women are underrepresented in academia's higher ranks. Promotion oftentimes requires positive student-provided course evaluations. At a U.S. university, both an archival and an experimental investigation uncovered gender discrimination that affected both men and women. A department's gender composition and the course levels being taught interacted to predict biases in evaluations. However, women were disproportionately impacted because women were more often in the gender minority. A subsequent audit of the university's promotion guidelines suggested a disproportionate impact on women's career trajectories. Our framework was guided by role congruity theory, which poses that workplace positions are gendered by the ratios of men and women who fill them. We hypothesized that students would expect educators in a department's gender majority to fill more so essential positions of teaching upper-level courses and those in the minority to fill more so supportive positions of teaching lower-level courses. Consistent with role congruity theory when an educator's gender violated expected gendered roles, we generally found discrimination in the form of lower evaluation scores. A follow-up experiment demonstrated that it was possible to change students' expectations about which gender would teach their courses. When we assigned students randomly to picture themselves as students in a male-dominated, female-dominated, or gender-parity department, we shifted their expectations of whether men or women would teach upper- and lower-level courses. Violating students' expectations created negative biases in teaching evaluations. This provided a causal link between department gender composition and discrimination. The importance of gender representation and ameliorating strategies are discussed.

Tissue-Specific Toxicokinetics of Aqueous Radium-226 in an Estuarine Mussel, Geukensia demissa.

Radiological contamination of coastal habitats poses potential risk for native fauna, but the bioavailability of aqueous radium (Ra) and other dissolved metals to marine bivalves remains unclear. This study was the first to examine the tissue-specific disposition of aqueous 226Ra in a coastal mussel, specifically the Atlantic ribbed mussel Geukensia demissa. Most organ groups reached steady-state concentrations within 7 days during experimental exposure, with an average uptake rate constant of 0.0013 mL g-1 d-1. When moved to Ra-free synthetic seawater, mussels rapidly eliminated aqueous 226Ra (average elimination rate constant 1.56 d-1). The biological half-life for aqueous 226Ra ranged from 8.9 h for the gills and labial palps to 15.4 h for the muscle. Although previous field studies have demonstrated notable 226Ra accumulation in the soft tissues of marine mussels and that, for freshwater mussels, tissue-incorporated 226Ra derives primarily from the aqueous phase, our tissue-specific bioconcentration factors (BCFs) were on the order of (8.3 ± 1.5) × 10-4 indicating low accumulation potential of aqueous 226Ra in estuarine mussels. This suggests marine and estuarine mussels obtain 226Ra from an alternate route, such as particulate-sorbed Ra ingested during filter-feeding or from a contaminated food source.

Functionalized Polymer Thin Films for Plutonium Capture and Isotopic Screening from Aqueous Sources.

The rapid screening of plutonium from aqueous sources remains a critical challenge for nuclear nonproliferation efforts. The determination of trace-level Pu isotopes in water requires offsite sample preparation and analysis; therefore, new methods that combine plutonium purification, concentration, and isotopic screening in a fieldable detection system will provide an invaluable tool for nuclear safeguards. This contribution describes the development and characterization of thin polymer-ligand films for the isolation and concentration of waterborne Pu for direct spectroscopic analyses. Submicron thin films were prepared through spin coating onto Si wafers and consisted of combinations of polystyrene (PS) with dibenzoylmethane, thenoyltrifluoroacetone, and di(2-ethylhexyl)phosphoric acid (HDEHP). Pu uptake studies from solutions at pH from 2.3 to 6.3 indicated that only films containing HDEHP exhibited significant recovery of Pu. High alpha spectroscopy peak energy resolutions were achieved for PS-HDEHP films over a range of film thicknesses from 30 to 250 nm. A separate study was performed to evaluate uptake from a primarily Pu(V) solution where it was observed that doubling the HDEHP loading in the film increased uptake of Pu by an order of magnitude. X-ray photoelectron spectroscopy (XPS) analysis revealed that HDEHP was highly concentrated within the first few nanometers of the film at the higher loading. XPS analysis also revealed that, in the presence of water, HDEHP was stripped from the surface layer of the film at circumneutral pH. While significant losses of ligand were seen in all samples, higher loadings of HDEHP resulted in measurable amounts of ligand retained after a 12-h soak in water. Findings of this study are being used to guide the development of thin-film composite membrane-based detection methods for the rapid, fieldable analysis of Pu in water.

Enthalpy of Uranium Adsorption onto Hematite.

The influence of temperature on the adsorption of metal ions at the solid-water interface is often overlooked, despite the important role that adsorption plays in metal-ion fate and transport in the natural environment where temperatures vary widely. Herein, we examine the temperature-dependent adsorption of uranium, a widespread radioactive contaminant, onto the ubiquitous iron oxide, hematite. The multitemperature batch adsorption data and surface complexation models indicate that the adsorption of uranium, as the hexavalent uranyl (UO22+) ion, increases significantly with increasing temperature, with an adsorption enthalpy (ΔHads) of +71 kJ mol-1. We suggest that this endothermic, entropically driven adsorption behavior is linked to reorganization of the uranyl-ion hydration and interfacial water structures upon UVI adsorption at the hematite surface. Overall, this work provides fundamental insight into the thermodynamics driving metal-ion adsorption reactions and provides the specific enthalpy value necessary for improved predictive geochemical modeling of UVI adsorption in the environment.

Dissolution and Vertical Transport of Uranium from Stable Mineral Forms by Plants as Influenced by the Co-occurrence of Uranium with Phosphorus.

Plants could mobilize (dissolution followed by vertical transport) uranium (U) from mineral forms that are otherwise stable. However, the variability of this plant-mediated mobilization of U as a function of the presence of various essential plant nutrients contained in these minerals remains unknown. A series of column experiments were conducted using Andropogon virginicus to quantify the vertical transport of U from stable mineral forms as influenced by the chemical and physical coexistence of U with the essential nutrient, phosphorus (P). The presence of plants significantly increased the vertical migration of U only when U was precipitated with P (UO2HPO4·4H2O; chernikovite) but not from UO2 (uraninite) that lacks any essential plant nutrient. The U dissolution was further increased when chernikovite co-occurred with a sparingly available form of P (FePO4) under P-limited growing conditions. Similarly, A. virginicus accumulated the highest amount of U from chernikovite (0.05 mg/g) in the presence of FePO4 compared to that of uraninite (no-P) and chernikovite supplemented with KH2PO4. These results signify an increased plant-mediated dissolution, uptake, and leaching of radioactive contaminants in soils that are nutrient deficient, a key factor that should be considered in management at legacy contamination sites.

Impact of Natural Organic Matter on Plutonium Vadose Zone Migration from an NH4Pu(V)O2CO3(s) Source.

We investigated the influence of natural organic matter (NOM) on the behavior of Pu(V) in the vadose zone through a combination of the field lysimeter and laboratory studies. Well-defined solid sources of NH4Pu(V)O2CO3(s) were placed in two 5-L lysimeters containing NOM-amended soil collected from the Savannah River Site (SRS) or unamended vadose zone soil and exposed to 3 years of natural South Carolina, USA, meteorological conditions. Lysimeter soil cores were removed from the field, used in desorption experiments, and characterized using wet chemistry methods and X-ray absorption spectroscopy. For both lysimeters, Pu migrated slowly with the majority (>95%) remaining within 2 cm of the source. However, without the NOM amendment, Pu was transported significantly farther than in the presence of NOM. Downward Pu migration appears to be influenced by the initial source oxidation state and composition. These Pu(V) sources exhibited significantly greater migration than previous studies using Pu(IV) or Pu(III) sources. However, batch laboratory experiments demonstrated that Pu(V) is reduced by the lysimeter soil in the order of hours, indicating that downward migration of Pu may be due to cycling between Pu(V) and Pu(IV). Under the conditions of these experiments, NOM appeared to both enhance reduction of the Pu(V) source as well as Pu sorption to soils. This indicates that NOM will tend to have a stabilizing effect on Pu migration under SRS vadose zone field conditions.

Thermodynamics and Electronic Properties of Heterometallic Multinuclear Actinide-Containing Metal-Organic Frameworks with "Structural Memory".

Thermodynamic studies of actinide-containing metal-organic frameworks (An-MOFs), reported herein for the first time, are a step toward addressing challenges related to effective nuclear waste administration. In addition to An-MOF thermochemistry, enthalpies of formation were determined for the organic linkers, 2,2'-dimethylbiphenyl-4,4'-dicarboxylic acid (H2Me2BPDC) and biphenyl-4,4'-dicarboxylic acid (H2BPDC), which are commonly used building blocks for MOF preparation. The electronic structure of the first example of An-MOF with mixed-metal AnAn'-nodes was influenced through coordination of transition metals as shown by the density of states near the Fermi edge, changes in the Tauc plot, conductivity measurements, and theoretical calculations. The "structural memory" effect (i.e., solvent-directed crystalline-amorphous-crystalline structural dynamism) was demonstrated as a function of node coordination degree, which is the number of organic linkers per metal node. Remarkable three-month water stability was reported for Th-containing frameworks herein, and the mechanism is also considered for improvement of the behavior of a U-based framework in water. Mechanistic aspects of capping linker installation were highlighted through crystallographic characterization of the intermediate, and theoretical calculations of free energies of formation (ΔGf) for U- and Th-MOFs with 10- and 12-coordinated secondary building units (SBUs) were performed to elucidate experimentally observed transformations during the installation processes. Overall, these results are the first thermochemical, electronic, and mechanistic insights for a relatively young class of actinide-containing frameworks.

Mobility of Aqueous and Colloidal Neptunium Species in Field Lysimeter Experiments.

Due to its radiotoxicity, long half-life, and potentially high environmental mobility, neptunium transport is of paramount importance for risk assessment and safety. Environmental transport of neptunium through field lysimeters at the Savannah River Site was observed from both oxidized (Np(V)) and reduced (Np(IV)) source materials. While transport from oxidized neptunium sources was expected, the unexpected transport from reduced neptunium sources spurred further investigation into transport mechanisms. Partial oxidation of the reduced neptunium source resulted in significant release and transport into the mobile aqueous phase, though a reduced colloidal neptunium species appears to have also been present, enhancing neptunium mobility over shorter distances. These field and laboratory experiments demonstrate the multiple controls on neptunium vadose zone transport and chemical behavior, as well as the need for thorough understanding of radionuclide source terms for long-term risk prediction.

Phosphorus Stress-Induced Changes in Plant Root Exudation Could Potentially Facilitate Uranium Mobilization from Stable Mineral Forms.

Apparent deficiency of soil mineral nutrients often triggers specific physio-morphological changes in plants, and some of these changes could also inadvertently increase the ability of plants to mobilize radionuclides from stable mineral forms. This work, through a series of sand-culture, hydroponics, and batch-equilibration experiments, investigated the differential ability of root exudates of Andropogon virginicus grown under conditions with variable phosphorus (P) availability (KH2PO4, FePO4, Ca3(PO4)2, and no P) to solubilize uranium (U) from the uranyl phosphate mineral Chernikovite. The mineral form of P, and hence the bioavailability of P, affected the overall composition of the root exudates. The lower bioavailable forms of P (FePO4 and Ca3(PO4)2), but not the complete absence of P, resulted in a higher abundance of root metabolites with chelating capacity at 72 hrs after treatment application. In treatments with lower P-bioavailability, the physiological amino acid concentration inside of the roots increased, whereas the concentration of organic acids in the roots decreased due to the active exudation. In batch dissolution experiments, the organic acids, but not amino acids, increase the dissolution U from Chernikovite. The root exudate matrix of plants exposed to low available forms of P induced a >60% increase in U dissolution from Chernikovite due to 5-16 times greater abundance of organic acids in these treatments. However, this was ca. 70% of the theoretical dissolution achievable by this exudate matrix. These results highlight the potential of using active management of soil P as an effective tool to alter the plant-mediated mobilization of U in contaminated soil.

Anion-Exchange Fibers for Improved Sample Loading in Ultra-Trace Analysis of Plutonium by Thermal Ionization Mass Spectrometry.

A new sample loading procedure was developed for isotope ratio measurements of ultratrace amounts of plutonium with thermal ionization mass spectrometry (TIMS). The goal was to determine the efficacy of a polymer fiber architecture for TIMS sample loading by following similar sample loading procedures as those used in bead loading. Fibers with diameter of approximately 100 µm were prepared from triethylamine-quaternized-poly(vinylbenzyl chloride) cross-linked with diazabicyclo[2.2.2]octane. Fiber sections (2.5 mm) were loaded with 10 pg of New Brunswick Laboratory certified reference material (NBL CRM) 128 from an 8 M HNO3 matrix and affixed to rhenium filaments with collodion. A single filament assembly was used for these analyses. Total ion counts (239Pu + 242Pu) and isotope ratios obtained from fiber-loaded filaments were compared to those measured by depositing Pu amended resin beads on the filament. Fiber loading was found to improve sensitivity, accuracy, and precision of isotope ratio measurements of plutonium when compared to the established resin bead loading method, while maintaining its simplicity. The average number of detected Pu+ counts was 180% greater, and there was a 72% reduction in standard deviation of ratio measurements when using fiber loading. An average deviation of 0.0012 (0.117%) from the certified isotope ratio value of NBL CRM Pu128 was measured when fiber loading versus a deviation of 0.0028 (0.284%) when bead loading. The fiber formation method presented in this study can be extended to other anion-exchange polymer chemistries and, therefore, offers a convenient platform to investigate the efficacy of novel polymer chemistries in sample loading for TIMS.

Effect of Natural Organic Matter on Plutonium Sorption to Goethite.

The effect of citric acid (CA), desferrioxamine B (DFOB), fulvic acid (FA), and humic acid (HA) on plutonium (Pu) sorption to goethite was studied as a function of organic carbon concentration and pH using batch sorption experiments at 5 mgC·L-1 and 50 mgC·L-1 natural organic matter (NOM), 10-9-10-10 M 238Pu, and 0.1 g·L-1 goethite concentrations, at pH 3, 5, 7, and 9. Low sorption of ligands coupled with strong Pu complexation decreased Pu sorption at pH 5 and 7, relative to a ligand-free system. Conversely, CA, FA, and HA increased Pu sorption to goethite at pH 3, suggesting ternary complex formation or, in the case of humic acid, incorporation into HA aggregates. Mechanisms for ternary complex formation were characterized by Fourier transform infrared spectroscopy in the absence of Pu. CA and FA demonstrated clear surface interactions at pH 3, HA appeared unchanged suggesting HA aggregates had formed, and no DFOB interactions were observed. Plutonium sorption decreased in the presence of DFOB (relative to a ligand free system) at all pH values examined. Thus, DFOB does not appear to facilitate formation of ternary Pu-DFOB-goethite complexes. At pH 9, Pu sorption in the presence of all NOM increased relative to pH 5 and 7; speciation models attributed this to Pu(IV) hydrolysis competing with ligand complexation, increasing sorption. The results indicate that in simple Pu-NOM-goethite ternary batch systems, NOM will decrease Pu sorption to goethite at all but particularly low pH conditions.

High-Resolution 4D Preclinical Single-Photon Emission Computed Tomography/X-ray Computed Tomography Imaging of Technetium Transport within a Heterogeneous Porous Media.

A dynamic 99mTc tracer experiment was performed to investigate the capabilities of combined preclinical single photon emission computed tomography (SPECT) and X-ray computed tomography (CT) for investigating transport in a heterogeneous porous medium. The experiment was conducted by continuously injecting a 99mTc solution into a column packed with eight layers (i.e., soil, silica gel, and 0.2-4 mm glass beads). Within the imaging results it was possible to correlate observed features with objects as small as 2 mm for the SPECT and 0.2 mm for the CT. Time-lapse SPECT imaging results illustrated both local and global nonuniform transport phenomena and the high-resolution CT data were found to be useful for interpreting the cause of variations in the 99mTc concentration associated with structural features within the materials, such as macropores. The results of this study demonstrate SPECT/CT as a novel tool for 4D (i.e., transient three-dimensional) noninvasive imaging of fate and transport processes in porous media. Despite its small scale, an experiment with such high resolution data allows us to better understand the pore scale transport which can then be used to inform larger scale studies.

A Novel Method for Tracer Concentration Plutonium(V) Solution Preparation.

Preparation of relatively pure low concentration Pu(V) solutions for environmental studies is nontrivial due to the complex redox chemistry of Pu. Ozone gas generated by an inexpensive unit designed for household-use was used to oxidize a 2 × 10(-8) M Pu(IV) solution to predominantly Pu(VI) with some Pu(V) present. Over several days, the Pu(VI) in the solution reduced to Pu(V) without further reducing to Pu(IV). The reduction from Pu(VI) to Pu(V) could be accelerated by raising the pH of the solution, which led to an immediate conversion without substantial conversion to Pu(IV). The aqueous Pu was found to be stable as predominately Pu(V) for greater than one month from pH 3-7; however, at circumneutral pH, a sizable fraction of Pu was lost from solution by either precipitation or sorption to the vial walls. This method provides a fast means of preparing Pu(V) solutions for tracer concentration studies without numerous extraction or cleanup steps.

Quantitative Measurement of Ligand Exchange with Small-Molecule Ligands on Iron Oxide Nanoparticles via Radioanalytical Techniques.

Ligand exchange on the surface of hydrophobic iron oxide nanoparticles is a common method for controlling surface chemistry for a desired application. Furthermore, ligand exchange with small-molecule ligands may be necessary to obtain particles with a specific size or functionality. Understanding to what extent ligand exchange occurs and what factors affect it is important for the optimization of this critical procedure. However, quantifying the amount of exchange may be difficult because of the limitations of commonly used characterization techniques. Therefore, we utilized a radiotracer technique to track the exchange of a radiolabeled 14C-oleic acid ligand with hydrophilic small-molecule ligands on the surface of iron oxide nanoparticles. Iron oxide nanoparticles functionalized with 14C-oleic acid were modified with small-molecule ligands with terminal functional groups including catechols, phosphonates, sulfonates, thiols, carboxylic acids, and silanes. These moieties were selected because they represent the most commonly used ligands for this procedure. The effectiveness of these molecules was compared using both procedures widely found in the literature and using a standardized procedure. After ligand exchange, the nanoparticles were analyzed using liquid scintillation counting (LSC) and inductively coupled plasma-mass spectrometry. The labeled and unlabeled particles were further characterized by transmission electron microscopy (TEM) and dynamic light scattering (DLS) to determine the particle size, hydrodynamic diameter, and zeta potential. The unlabeled particles were characterized via attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and vibrating sample magnetometry (VSM) to confirm the presence of the small molecules on the particles and verify the magnetic properties, respectively. Radioanalytical determination of 14C-oleic acid was used to calculate the total amount of oleic acid remaining on the surface of the particles after ligand exchange. The results revealed that the ligand-exchange reactions performed using widely cited procedures did not go to completion. Residual oleic acid remained on the particles after these reactions and the reactions using a standardized protocol. A comparison of the ligand-exchange procedures indicated that the binding moiety, multidenticity, reaction time, temperature, and presence of a catalyst impacted the extent of exchange. Quantification of the oleic acid remaining after ligand exchange revealed a binding hierarchy in which catechol-derived anchor groups displace the most oleic acid on the surface of the nanoparticles and the thiol group displaces the least amount of oleic acid. Thorough characterization of ligand exchange is required to develop nanoparticles suitable for their intended application.

Effects of Titanium Doping in Titanomagnetite on Neptunium Sorption and Speciation.

Neptunium-237 is a radionuclide of great interest owing to its long half-life (2.14 × 10(6) years) and relative mobility as the neptunyl ion (NpO2(+)) under many surface and groundwater conditions. Reduction to tetravalent neptunium (Np(IV)) effectively immobilizes the actinide in many instances due to its low solubility and strong interactions with natural minerals. One such mineral that may facilitate the reduction of neptunium is magnetite (Fe(2+)Fe(3+)2O4). Natural magnetites often contain titanium impurities which have been shown to enhance radionuclide sorption via titanium's influence on the Fe(2+)/Fe(3+) ratio (R) in the absence of oxidation. Here, we provide evidence that Ti-substituted magnetite reduces neptunyl species to Np(IV). Titanium-substituted magnetite nanoparticles were synthesized and reacted with NpO2(+) under reducing conditions. Batch sorption experiments indicate that increasing Ti concentration results in higher Np sorption/reduction values at low pH. High-resolution transmission electron microscopy of the Ti-magnetite particles provides no evidence of NpO2 nanoparticle precipitation. Additionally, X-ray absorption spectroscopy confirms the nearly exclusive presence of Np(IV) on the titanomagnetite surface and provides supporting data indicating preferential binding of Np to terminal Ti-O sites as opposed to Fe-O sites.