Design of electrochemical processes for treatment of unusual waste streams

UCRL- JC- 129438 PREPRINT This document was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor the University of California nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or the University of California. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or the University of California, and shall not be used for advertising or product endorsement purposes. Introduction. An overview of work done on the development of three electrochemical processes that meet the specific needs of low- level waste treatment is presented. These technologies include: mediated electrochemical oxidation [I- 4]; bipolar membrane electrodialysis [5]; and electrosorption of carbon aerogel electrodes [6- 9]. Design strategies are presented to assess the suitability of these electrochemical processes for Mediated electrochemical oxidation. Mixed wastes include both hazardous and radioactive components. It is desirable to reduce the overall volume of the waste before immobilization and disposal in repositories. While incineration is an attractive technique for the destruction of organic fractions of mixed wastes, such high-temperature thermal processes pose the threat of volatilizing various radionuclides. By destroying organics in the aqueous phase at low temperature and ambient pressure, the risk of volatilization can be reduced. One approach that is attractive is the use of eiectrochemically generated mediators such as Ag( ll), Co( Ill) and Fe( III). These oxidants react with organicsin Bipolar membrane electrodialysis. in the aqueous processing of nuclear materials, process steps arise that require the neutralization of an acidic stream with a strong base. Ultimately, these neutralized salt solutions become aqueous waste streams, requiring further treatment and disposal. By "splitting" such neutralized salt solutions into their acid and base components, the generation of aqueous mixed waste can be greatly reduced. At LLNL, a bipolar membrane electrodialysis cell has been used to separate neutral solutions of NaCl, NaNO1 and Na, SO, into product streams of NaOH, HCI, HNOj and H2S0,, which could be recycled. The eftlciency of this particular process will be discussed, as well as practical limitations of the technology. Basic principles of engineering design of such systems will be reviewed

Localized corrosion and stress corrosion cracking of candidate materials for high-level radioactive waste disposal containers in the US: A literature review

Container materials may undergo any of several modes of degradation in this environment, including: undesirable phase transformations due to lack of phase stability; atmospheric oxidation; general aqueous corrosion; pitting; crevice corrosion; intergranular stress corrosion cracking (IGSCC); and transgranular stress corrosion cracking (TGSCC). This paper is an analysis of data from the literature relevant to the pitting, crevice corrosion, and stress corrosion cracking (SCC) of these alloys. Though all three austenitic candidates have demonstrated pitting and crevice corrosion in chloride-containing environments, Alloy 825 has the greatest resistance to these forms of localized attack. Both types 304L and 316L stainless steels are susceptible to SCC in acidic chloride media. In contrast, SCC has not been documented for Alloy 825 under comparable conditions. Gamma irradiation has been found to enhance SCC of Types 304 and 304L stainless steels, but it has no detectable effect on the resistance of Alloy 825 to SCC. Furthermore, while microbiologically induced corrosion effects have been observed for 300-series stainless steels, nickel-based alloys such as Alloy 825 seem to be immune to such problems. Of the copper-based alloys, CDA 715 has the best overall resistance to localized attack. Its resistance to pitting is comparable to that of CDA 613 and superior to that of CDA 102. Observed rates of dealloying in CDA 715 are less than those observed in CDA 613 by orders of magnitude. The resistance of CDA 715 to SCC in tarnishing ammonical environments is comparable to that of CDA 102 and superior to that of CDA 613. Its resistance to SCC in nontarnishing ammonical environments is comparable to that of CDA 613 and superior to that of CDA 102. 22 refs., 8 figs., 4 tabs

Modeling the corrosion of high-level waste containers: CAM-CRM interface

A key component of the Engineered Barrier System (EBS) being designed for containment of spent-fuel and high-level waste at the proposed geological respository at Yucca Mountain, Nevada is a two-layer canister. In this particular design, the inner barrier is made of a corrosion resistant material (CRM) such as Alloy 825, 625 or C-22, while the outer barrier is made of a corrosion-allowance material (CAM) such as A516 or Monel 400. At the present time, Alloy C-22 and A516 are favored. This publication addresses the development of models to account for corrosion of Alloy C-22 surfaces exposed directly to the Near Field Environmental (NFE), as well as to the exacerbated conditions in the CAM-CRM crevice

Survey of degradation modes of candidate materials for high-level radioactive-waste disposal containers; Overview

Three iron- to nickel-based austenitic alloys and three copper-based alloys are being considered as candidate materials for the fabrication of high-level radioactive-waste disposal containers. The austenitic alloys are Types 304L and 316L stainless steels and the high-nickel material Alloy 825. The copper-based alloys are CDA 102 (oxygen-free copper), CDA 613 (Cu-7Al), and CDA 715 (Cu-30Ni). Waste in the forms of both spent fuel assemblies from reactors and borosilicate glass will be sent to the prospective repository at Yucca Mountain, Nevada. The decay of radionuclides will result in the generation of substantial heat and gamma radiation. Container materials may undergo any of several modes of degradation in this environment, including undesirable phase transformations due to a lack of phase stability; atmospheric oxidation; general aqueous corrosion; pitting; crevice corrosion; intergranular stress corrosion cracking; and transgranular stress corrosion cracking. Problems specific to welds, such as hot cracking, may also occur. A survey of the literature has been prepared as part of the process of selecting, from among the candidates, a material that is adequate for repository conditions. The modes of degradation are discussed in detail in the survey to determine which apply to the candidate alloys and the extent to which they may actually occur. The eight volumes of the survey are summarized in Sections 1 through 8 of this overview. The conclusions drawn from the survey are also given in this overview

Sputter Deposition of Semiconductor Superlattices for Thermoelectric Applications

Theoretical dramatic improvement of the thermoelectric properties of materials by using quantum confinement in novel semiconductor nanostructures has lead to considerable interest in the thermoelectric community. Therefore, we are exploring the critical materials issues for fabrication of quantum confined structures by magnetron sputtering in the lead telluride and bismuth telluride families of materials. We have synthesized modulated structures from thermoelectric materials with bilayer periods of as little as 3.2 nm and shown that they are stable at deposition temperatures high enough to grow quality films. Issues critical to high quality film growth have been investigated such as nucleation and growth conditions and their effect on crystal orientation and growth morphology. These investigations show that nucleating the film at a temperature below the growth temperature of optimum electronic properties produces high quality films. Our work with sputter deposition, which is inherently a high rate deposition process, builds the technological base necessary to develop economical production of these advanced materials. High deposition rate is critical since, even if efficiencies comparable with CFC based refrigeration systems can be achieved, large quantities of quantum confined materials will be necessary for cost-competitive uses

Is there anybody out there? Occupancy of the carnivore guild in a temperate archipelago

Carnivores are important components of ecological communities with wide-ranging effects that vary with carnivore size, natural history, and hunting tactics. Researchers and managers should strive to understand both the presence and distribution of carnivores within their local environment. We studied the carnivore guild in the Apostle Islands, where the distribution and occupancy of carnivores was largely unknown. We monitored 19 islands with 160 functioning camera traps from 2014-2017, from which we collected 203,385 photographs across 49,280 trap nights. We documented 7,291 total wildlife events with 1,970 carnivore events, and detected 10 of the 12 terrestrial carnivores found in Wisconsin. Detection rates for species were generally higher in summer than winter, except for coyotes (Canis latrans) and red foxes (Vulpes vulpes). Finitesample occupancy estimates for carnivores varied across islands, with mean estimated occupancy across islands varying from a high of 0.73 for black bears to a low of 0.21 for gray wolves. Of the potential island biogeography explanatory variables for carnivore occupancy we considered, island size was the most important, followed by distance to the mainland, and then interisland distance. We estimated that terrestrial carnivore species varied in the number of islands they were detected on from 1 island for gray wolves to 13 islands for black bears. Estimated carnivore richness across islands (i.e., the number of carnivores occupying an island) also varied substantively from 1 species on Michigan Island to 10 species on Stockton Island. Island size and connectivity between islands appear important for the persistence of the carnivore community in the Apostle Islands

CSF1R inhibitor JNJ-40346527 attenuates microglial proliferation and neurodegeneration in P301S mice

Neuroinflammation and microglial activation are significant processes in Alzheimer's disease pathology. Recent genome-wide association studies have highlighted multiple immune-related genes in association with Alzheimer's disease, and experimental data have demonstrated microglial proliferation as a significant component of the neuropathology. In this study, we tested the efficacy of the selective CSF1R inhibitor JNJ-40346527 (JNJ-527) in the P301S mouse tauopathy model. We first demonstrated the anti-proliferative effects of JNJ-527 on microglia in the ME7 prion model, and its impact on the inflammatory profile, and provided potential CNS biomarkers for clinical investigation with the compound, including pharmacokinetic/pharmacodynamics and efficacy assessment by TSPO autoradiography and CSF proteomics. Then, we showed for the first time that blockade of microglial proliferation and modification of microglial phenotype leads to an attenuation of tau-induced neurodegeneration and results in functional improvement in P301S mice. Overall, this work strongly supports the potential for inhibition of CSF1R as a target for the treatment of Alzheimer's disease and other tau-mediated neurodegenerative diseases

Inflammatory biomarkers in Alzheimer's disease plasma

Introduction: Plasma biomarkers for Alzheimer's disease (AD) diagnosis/stratification are a \u201cHoly Grail\u201d of AD research and intensively sought; however, there are no well-established plasma markers. Methods: A hypothesis-led plasma biomarker search was conducted in the context of international multicenter studies. The discovery phase measured 53 inflammatory proteins in elderly control (CTL; 259), mild cognitive impairment (MCI; 199), and AD (262) subjects from AddNeuroMed. Results: Ten analytes showed significant intergroup differences. Logistic regression identified five (FB, FH, sCR1, MCP-1, eotaxin-1) that, age/APO\u3b54 adjusted, optimally differentiated AD and CTL (AUC: 0.79), and three (sCR1, MCP-1, eotaxin-1) that optimally differentiated AD and MCI (AUC: 0.74). These models replicated in an independent cohort (EMIF; AUC 0.81 and 0.67). Two analytes (FB, FH) plus age predicted MCI progression to AD (AUC: 0.71). Discussion: Plasma markers of inflammation and complement dysregulation support diagnosis and outcome prediction in AD and MCI. Further replication is needed before clinical translation

National identity predicts public health support during a global pandemic

Changing collective behaviour and supporting non-pharmaceutical interventions is an important component in mitigating virus transmission during a pandemic. In a large international collaboration (Study 1, N = 49,968 across 67 countries), we investigated self-reported factors associated with public health behaviours (e.g., spatial distancing and stricter hygiene) and endorsed public policy interventions (e.g., closing bars and restaurants) during the early stage of the COVID-19 pandemic (April-May 2020). Respondents who reported identifying more strongly with their nation consistently reported greater engagement in public health behaviours and support for public health policies. Results were similar for representative and non-representative national samples. Study 2 (N = 42 countries) conceptually replicated the central finding using aggregate indices of national identity (obtained using the World Values Survey) and a measure of actual behaviour change during the pandemic (obtained from Google mobility reports). Higher levels of national identification prior to the pandemic predicted lower mobility during the early stage of the pandemic (r = −0.40). We discuss the potential implications of links between national identity, leadership, and public health for managing COVID-19 and future pandemics.publishedVersio