Cast Stone Oxidation Front Evaluation: Preliminary Results For Samples Exposed To Moist Air

The rate of oxidation is important to the long-term performance of reducing salt waste forms because the solubility of some contaminants, e.g., technetium, is a function of oxidation state. TcO{sub 4}{sup −} in the salt solution is reduced to Tc(IV) and has been shown to react with ingredients in the waste form to precipitate low solubility sulfide and/or oxide phases. Upon exposure to oxygen, the compounds containing Tc(IV) oxidize to the pertechnetate ion, Tc(VII)O{sub 4}{sup −}, which is very soluble. Consequently the rate of technetium oxidation front advancement into a monolith and the technetium leaching profile as a function of depth from an exposed surface are important to waste form performance and ground water concentration predictions. An approach for measuring contaminant oxidation rate (effective contaminant specific oxidation rate) based on leaching of select contaminants of concern is described in this report. In addition, the relationship between reduction capacity and contaminant oxidation is addressed. Chromate (Cr(VI) was used as a non-radioactive surrogate for pertechnetate, Tc(VII), in Cast Stone samples prepared with 5 M Simulant. Cast Stone spiked with pertechnetate was also prepared and tested. Depth discrete subsamples spiked with Cr were cut from Cast Stone exposed to Savannah River Site (SRS) outdoor ambient temperature fluctuations and moist air. Depth discrete subsamples spiked with Tc-99 were cut from Cast Stone exposed to laboratory ambient temperature fluctuations and moist air. Similar conditions are expected to be encountered in the Cast Stone curing container. The leachability of Cr and Tc-99 and the reduction capacities, measured by the Angus-Glasser method, were determined for each subsample as a function of depth from the exposed surface. The results obtained to date were focused on continued method development and are preliminary and apply to the sample composition and curing / exposure conditions described in this report. The Cr oxidation front (depth to which soluble Cr was detected) for the Cast Stone sample exposed for 68 days to ambient outdoor temperatures and humid air (total age of sample was 131 days) was determined to be about 35 mm below the top sample surface exposed. The Tc oxidation front, depth at which Tc was insoluble, was not determined. Interpretation of the results indicates that the oxidation front is at least 38 mm below the exposed surface. The sample used for this measurement was exposed to ambient laboratory conditions and humid air for 50 days. The total age of the sample was 98 days. Technetium appears to be more easily oxidized than Cr in the Cast Stone matrix. The oxidized forms of Tc and Cr are soluble and therefore leachable. Longer exposure times are required for both the Cr and Tc spiked samples to better interpret the rate of oxidation. Tc spiked subsamples need to be taken further from the exposed surface to better define and interpret the leachable Tc profile. Finally Tc(VII) reduction to Tc(IV) appears to occur relatively fast. Results demonstrated that about 95 percent of the Tc(VII) was reduced to Tc(IV) during the setting and very early stage setting for a Cast Stone sample cured 10 days. Additional testing at longer curing times is required to determine whether additional time is required to reduce 100 % of the Tc(VII) in Cast Stone or whether the Tc loading exceeded the ability of the waste form to reduce 100 % of the Tc(VII). Additional testing is required for samples cured for longer times. Depth discrete subsampling in a nitrogen glove box is also required to determine whether the 5 percent Tc extracted from the subsamples was the result of the sampling process which took place in air. Reduction capacity measurements (per the Angus-Glasser method) performed on depth discrete samples could not be correlated with the amount of chromium or technetium leached from the depth discrete subsamples or with the oxidation front inferred from soluble chromium and technetium (i.e., effective Cr and Tc oxidation fronts). Residual reduction capacity in the oxidized region of the test samples indicates that the remaining reduction capacity is not effective in re-reducing Cr(VI) or Tc(VII) in the presence of oxygen. Depth discrete sampling and leaching is a useful for evaluating Cast Stone and other chemically reducing waste forms containing ground granulated blast furnace slag (GGBFS) or other reduction / sequestration reagents to control redox sensitive contaminant chemistry and leachability in the near surface disposal environment. Based on results presented in this report, reduction capacity measured by the Angus-Glasser Ce(IV) method is not an appropriate or meaningful parameter for determining or predicting Tc and Cr oxidation / retentions, speciation, or solubilities in cementitious materials such as Cast Stone. A model for predicting Tc(IV) oxidation to soluble Tc(VII) should consider the waste form porosity (pathway for oxygen ingress), oxygen source, and the contaminant specific oxidation rates and oxidation fronts. Depth discrete sampling of materials exposed to realistic conditions in combination with short term leaching of crushed samples has potential for advancing the understanding of factors influencing performance. This information can be used to support conceptual model development

Parametric ordering of complex systems

Cellular automata (CA) dynamics are ordered in terms of two global parameters, computable {\sl a priori} from the description of rules. While one of them (activity) has been used before, the second one is new; it estimates the average sensitivity of rules to small configurational changes. For two well-known families of rules, the Wolfram complexity Classes cluster satisfactorily. The observed simultaneous occurrence of sharp and smooth transitions from ordered to disordered dynamics in CA can be explained with the two-parameter diagram

Dismissive incomprehension: a use of purported ignorance to undermine others

This paper analyses a particular social phenomenon whereby a speaker purports ignorance of the meaning of another speaker’s speech in order to undermine that other speaker: dismissive incomprehension. It develops a speech act theory of the phenomenon, and develops its distinctive, and sometimes problematic perlocutionary character. After taking a look at some of the issues surrounding the phenomenon, the paper compares it to more fully studied features of our social lives, including epistemic injustice and gaslighting. It ends with some thoughts on counteracting the problematic cases of dismissive incomprehension

Access to and experience of education for children and adolescents with cancer: a scoping review protocol

BACKGROUND: Cancer diagnosis in childhood or adolescence impacts significantly on school attendance, experience and educational outcomes. While there is longstanding recognition in clinical practice that these effects span the whole illness trajectory and continue beyond treatment completion, further clarity is required on the specific barriers and facilitators to education during cancer treatment and beyond, as well as on the experiences of children and adolescents across the full range of education settings (hospital, home, virtual, original school of enrolment), in order to determine which interventions are successful in improving access and experience from their perspective. The aim of this review is to identify what is known from the existing literature about access to and experience of education for children and adolescents with cancer during and post treatment. METHODS: We have planned a scoping literature review searching the following databases from inception onwards: MEDLINE (Ovid), Embase and Embase Classic, Web of Science Core Collection, Education Resources Index, Sociological Abstracts, APA PsycINFO, SCOPUS, CINAHL Plus, Emcare and The Cochrane Library. In addition, DARE, conference abstracts, key journals, and institutional websites will be searched. Arksey and O'Malley's six-step process will be followed, including a consultation exercise. Studies, reports and policies from any country providing care and treatment for children and adolescents with cancer published in English will be considered eligible for inclusion. Two reviewers will independently screen all citations, full-text articles and abstract data. A narrative summary of findings will be conducted. Data analysis will involve quantitative (e.g., frequencies) and qualitative (e.g., content and thematic analysis) methods. DISCUSSION: This is a timely examination given the increased incidence of childhood cancer, more intensive treatment regimens and improved survival rates for childhood cancer. The inclusion of a substantive consultation exercise with families and professionals will provide an important opportunity to examine the scoping review outputs. Findings will assist the childhood cancer community in developing a comprehensive evidence-based understanding of a significant associated bio-psychosocial impact of cancer diagnosis and treatment and will form the first step towards developing effective interventions and policies to mitigate identified detrimental effects. SYSTEMATIC REVIEW REGISTRATION: Open Science Framework (osf/io/yc4wt)

Boundary line models for soil nutrient concentrations and wheat yield in national-scale datasets

In boundary line analysis a biological response (e.g., crop yield) is assumed to be a function of a variable (e.g., soil nutrient concentration), which limits the response in only some subset of observations because other limiting factors also apply. The response function is therefore expressed by an upper boundary of the plot of the response against the variable. This model has been used in various branches of soil science. In this paper we apply it to the analysis of some large datasets, originating from commercial farms in England and Wales, on the recorded yield of wheat and measured concentrations of soil nutrients in within‐field soil management zones. We considered boundary line models for the effects of potassium (K), phosphorus (P) and magnesium (Mg) on yield, comparing the model with a simple bivariate normal distribution or a bivariate normal censored at a constant maximum yield. We were able to show, using likelihood‐based methods, that the boundary line model was preferable in most cases. The boundary line model suggested that the standard RB209 soil nutrient index values (Agriculture and Horticulture Development Board, nutrient management guide (RB209), 2017) are robust and apply at the within‐field scale. However, there was evidence that wheat yield could respond to additional Mg at concentrations above index 0, contrary to RB209 guidelines. Furthermore, there was evidence that the boundary line model for yield and P differs between soils at different pH and depth intervals, suggesting that shallow soils with larger pH require a larger target P index than others

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Assessing the impact of verbal and visuospatial working memory load on eye-gaze cueing

Observers tend to respond more quickly to peripheral stimuli that are being gazed at by a centrally presented face, than to stimuli that are not being gazed at. While this gaze-cueing effect was initially seen as reflexive, there have also been some indications that top-down control processes may be involved. Therefore, the present investigation employed a dual-task paradigm to attempt to disrupt the putative control processes involved in gaze cueing. Two experiments examined the impact of working memory load on gaze cueing. In Experiment 1, participants were required to hold a set of digits in working memory during each gaze trial. In Experiment 2, the gaze task was combined with an auditory task that required the manipulation and maintenance of visuo-spatial information. Gaze cueing effects were observed, but they were not modulated by dual-task load in either experiment. These results are consistent with traditional accounts of gaze cueing as a highly reflexive process

Atmospheric Circulation of Eccentric Hot Neptune GJ436b

GJ436b is a unique member of the transiting extrasolar planet population being one of the smallest and least irradiated and possessing an eccentric orbit. Because of its size, mass and density, GJ436b could plausibly have an atmospheric metallicity similar to Neptune (20-60 times solar abundances), which makes it an ideal target to study the effects of atmospheric metallicity on dynamics and radiative transfer in an extrasolar planetary atmosphere. We present three-dimensional atmospheric circulation models that include realistic non-gray radiative transfer for 1, 3, 10, 30, and 50 times solar atmospheric metallicity cases of GJ436b. Low metallicity models (1 and 3 times solar) show little day/night temperature variation and strong high-latitude jets. In contrast, higher metallicity models (30 and 50 times solar) exhibit day/night temperature variations and a strong equatorial jet. Spectra and light curves produced from these simulations show strong orbital phase dependencies in the 50 times solar case and negligible variations with orbital phase in the 1 times solar case. Comparisons between the predicted planet/star flux ratio from these models and current secondary eclipse measurements support a high metallicity atmosphere (30-50 times solar abundances) with disequilibrium carbon chemistry at play for GJ436b. Regardless of the actual atmospheric composition of GJ436b, our models serve to illuminate how metallicity influences the atmospheric circulation for a broad range of warm extrasolar planets.Comment: 25 pages, 13 figure

Eulerian Walkers as a model of Self-Organised Criticality

We propose a new model of self-organized criticality. A particle is dropped at random on a lattice and moves along directions specified by arrows at each site. As it moves, it changes the direction of the arrows according to fixed rules. On closed graphs these walks generate Euler circuits. On open graphs, the particle eventually leaves the system, and a new particle is then added. The operators corresponding to particle addition generate an abelian group, same as the group for the Abelian Sandpile model on the graph. We determine the critical steady state and some critical exponents exactly, using this equivalence.Comment: 4 pages, RevTex, 4 figure