Engineering topics

Nichols, Ralph

Publications and source records attributed to Nichols, Ralph.

4 records

DOE OSTI2023

Presence of aromatic-rich organic matter and its characterization in grout materials: Implications for radionuclide immobilization

Grout materials are commonly used to immobilize low-level radioactive waste. Organic moieties can be unintentionally present in common ingredients used to make these grout waste forms, which may result in the formation of organo-radionuclide species. These species can positively or negatively affect the immobilization efficiency. However, the presence of organic carbon compounds is rarely considered in models or characterized chemically. Here, we quantify the organic pool of grout formulations with and without slag, as well as the individual dry ingredients used to make the grout samples (ordinary Portland cement (OPC), slag and fly ash), including total organic carbon (TOC) and black carbon, followed by aromaticity evaluation and molecular characterization via Electro Spray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FTICRMS). All dry grout ingredients contained significant amounts of organic carbon, ranging from 550 mg/kg to 6250 mg/kg for the TOC pool, with an averaged abundance of 2933 ± 2537 mg/kg, of which 60 ± 29% was composed of black carbon. The significant abundance of a black carbon pool implies the presence of the aromatic-like compounds, which was further identified by both phosphate buffer-assisted aromaticity evaluation (e.g., >1000 mg-C/kg as aromatic-like carbon in the OPC) and dichloromethane (DCM) extraction with ESIFTICRMS analysis. Besides aromatic-like compounds, other organic moieties were also detected in the OPC, such as carboxyl-containing aliphatic molecules. While the organic compound only consists of minor fractions of the grout materials investigated, our observations of the presence of various radionuclide-binding organic moieties suggests the potential formation of organo-radionuclides, such as radioiodine, which might be present at lower molar concentrations than TOC. Here, evaluating the role of organic carbon complexation in controlling the disposed radionuclides, especially for those radionuclides with strong association with organic carbon, has important implications for the long-term immobilization of radioactive waste in grout systems.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Evaluation of Degradation Mechanisms for Solid Secondary Waste Grout Waste Forms

The overall objective of this work is to provide defensibility for the long-term performance of grouted Hanford SSW streams when disposed in a near surface disposal facility, IDF, on the Hanford Site. Providing defensibly for the long-term performance of the grouted waste forms is consistent with the research and development activities identified in the Performance Assessment Maintenance Plan, (Westcott et al. 2019), that are necessary to address the assumptions made in the PA. Specifically, this work addresses two areas identified for further research and development activities in the plan: (1) “Evaluate ongoing research on transport characteristics of cementitious materials using accelerated tests to approximate the effects of aging/alteration/weathering”; and (2) “Evaluate ongoing research on microbial effects on transport processes in cementitious materials.” The assembled subject matter expert team evaluated a list of degradation mechanisms and supporting processes and provided rankings of areas where further research and development (R&D) are needed. From this assessment, high priority R&D areas include: (1) the effects of carbonation, Ca leaching, and SSW dimensional change in grout waste forms; (2) updated model representations of grouted waste forms; and (3) scaled testing demonstrations. Moderate priority items including a paper study on possible microbial influence, reoxidation rates, radionuclide/contaminant dissolution from SSW in the grout and freeze thaw behavior. Other processes evaluated were either deemed unlikely to occur, to have little impact on the SSW waste forms, or to occur at time frames beyond those considered (>10,000 years). The assessments and proposed R&D approaches are expected to support an update to the WRPS SSW roadmap.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

Large seasonal fluctuations of groundwater radioiodine speciation and concentrations in a riparian wetland in South Carolina

Recent studies evaluating multiple years of groundwater radioiodine ( 129 I) concentration in a riparian wetland located in South Carolina, USA identified strong seasonal concentration fluctuations, such that summer concentrations were much greater than winter concentrations. These fluctuations were observed only in the wetlands but not in the upland portion of the plume and only with 129 I, and not with other contaminants of anthropogenic origin: nitrate/nitrite, strontium-90, technecium-99, tritium, or uranium. This unexplained observation was hypothesized to be the result of strongly coupled processes involving hydrology, water temperature, microbiology, and chemistry. To test this hypothesis, an extensive historical groundwater database was evaluated, and additional measurements of total iodine and iodine speciation were made from recently collected samples. During the summer, the water table decreased by as much as 0.7 m, surface water temperature increased by as much as 15 °C, and total iodine concentrations were consistently greater (up to 680%) than the following winter months. Most of the additional iodine observed in the summer could be attributed to proportional gains in organo-iodine, and not iodide or iodate. Furthermore, 129 I concentrations were observed to be two-orders-of-magnitude greater at the bottom of the upland aquifer than at the top. A coupled hydrological and biogeochemical conceptual model is proposed to tie these observations together. First, as the surface water temperature increased during the summer, microbial activity was enhanced, which in turn stimulated the formation of mobile organo-I. Hydrological processes were also likely involved in the observed iodine seasonal changes: (1) as the water table decreased in summer, the remaining upland water entering the wetland was comprised of a greater proportion of water containing elevated iodine concentrations from the low depths, and (2) water flow paths in summer changed such that the wells intercepted more of the contaminant plume and less of the diluting rainwater (due to evapotranspiration) and streamwater (as the lower levels promote a predominantly recharging system). Furthermore, these results underscore the importance of coupled processes influencing contaminant concentrations, and the need to assess seasonal contaminant variations to optimize long-term monitoring programs of wetlands.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1987

Gas filter correlation radiometry: Report of panel

To measure the concentration of a gas in the troposphere, the gas filter radiometer correlates the pattern of the spectral lines of a sample of gas contained within the instrument with the pattern of the spectral lines in the upwelling radiation. A schematic diagram of a generalized gas filter radiometer is shown. Three instruments (the Gas Filter Radiometer, GFR; the Halogen Occultation Experiment, HALOE; and the Gas Filter Correlation Spectrometer, GASCOFIL) that have application to remotely measuring tropospheric constituents are described. A set of preliminary calculations to determine the feasibility of performing a multiple-layer, tropospheric carbon monoxide measurement experiment was performed. It can be seen that a three-layer measurement in the troposphere is possible.

Reichle, Henry G., Jr.↗