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Thomas, David J.

Publications and source records attributed to Thomas, David J..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Plumbojarosite Remediation of Soil Affects Lead Speciation and Elemental Interactions in Soil and in Mice Tissues

Lead (Pb) contamination of soils is of global concern due to the devastating impacts of Pb exposure in children. Because early-life exposure to Pb has long-lasting health effects, reducing exposure in children is a critical public health goal that has intensified research on the conversion of soil Pb to low bioavailability phases. Recently, plumbojarosite (PLJ) conversion of highly available soil Pb was found to decrease Pb relative bioavailability (RBA <10%). However, there is sparse information concerning interactions between Pb and other elements when contaminated soil, pre- and post-remediation, is ingested and moves through the gastrointestinal tract (GIT). Addressing this may inform drivers of effective chemical remediation strategies. In this study, we utilize bulk and micro-focused Pb X-ray absorption spectroscopy to probe elemental interactions and Pb speciation in mouse diet, cecum, and feces samples following ingestion of contaminated soils pre- and post-PLJ treatment. RBA of treated soils was less than 1% with PLJ phases transiting the GIT with little absorption. In contrast, Pb associated with organics was predominantly found in the cecum. These results are consistent with transit of insoluble PLJ to feces following ingestion. The expanded understanding of Pb interactions during GIT transit complements our knowledge of elemental interactions with Pb that occur at higher levels of biological organization.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Bioavailable soil Pb minimized by in situ transformation to plumbojarosite

Exposure to lead (Pb) during early life has persistent adverse health effects. During childhood, ingestion of bioavailable Pb in contaminated soils can be a major route of Pb absorption. Remediation to alter physiochemical properties of soil-borne Pb can reduce Pb bioavailability. Our laboratory-based approach for soil Pb remediation uses addition of iron (Fe) sulfate and application of heat to promote formation of plumbojarosite (PLJ), a sparingly soluble Pb-Fe hydroxysulfate mineral. We treated two soils with anthropogenic Pb contamination and samples of clean topsoil spiked with various Pb compounds (i.e., carbonate, chloride, phosphate [P], or sulfate) to convert native Pb species to PLJ and used a mouse assay to assess relative bioavailability (RBA) of Pb in untreated (U) and remediated soils. Bone and blood Pb levels were significantly lower (P < 0.001, Student's t test) in mice that consumed diets amended with remediated soils than with U soils. Estimated RBA for Pb in both remediated natural soils and Pb-mineral spiked soils were reduced by >90% relative to Pb RBA for U soils, which is substantially more effective than other soil amendments, including P. X-ray absorption spectroscopy showed that >90% of all Pb species in remediated soils were converted to PLJ, and ingested PLJ was not chemically transformed during gastrointestinal tract transit. Post treatment neutralization of soil pH did not affect PLJ stability, indicating the feasibility in field conditions. These results suggest that formation of PLJ in contaminated soils can reduce the RBA of Pb and minimize this medium’s role as a source of Pb exposure for young children.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Long-Term in Situ Reduction in Soil Lead Bioavailability Measured in a Mouse Model

In this study, effects of different treatments on the bioavailability of lead (Pb) in soil from a smelter emission contaminated site in Joplin, Missouri, were evaluated in a mouse model. Similar estimates of relative bioavailability for Pb in untreated or treated soil were obtained in mice and in the well-established juvenile swine model. In the mouse model, treatments that used phosphate (phosphoric acid or triple superphosphate) combined with iron oxide or biosolids compost significantly reduced soil Pb bioavailability. Notably, effects of these remediation procedures were persistent, given that up to 16 years had elapsed between soil treatment and sample collection. Remediation of soils was associated with changes in Pb species present in soil. Differences in Pb species in ingested soil and in feces from treated mice indicated that changes in Pb speciation occurred during transit through the gastrointestinal tract. Use of the mouse model facilitates evaluation of remediation procedures and allows monitoring of the performance of procedures under laboratory and field conditions.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2012

Methylation of arsenic by recombinant human wild-type arsenic (+ 3 oxidation state) methyltransferase and its methionine 287 threonine (M287T) polymorph: Role of glutathione

Arsenic (+ 3 oxidation state) methyltransferase (AS3MT) is the key enzyme in the pathway for methylation of arsenicals. A common polymorphism in the AS3MT gene that replaces a threonyl residue in position 287 with a methionyl residue (AS3MT/M287T) occurs at a frequency of about 10% among populations worldwide. Here, we compared catalytic properties of recombinant human wild-type (wt) AS3MT and AS3MT/M287T in reaction mixtures containing S-adenosylmethionine, arsenite (iAs{sup III}) or methylarsonous acid (MAs{sup III}) as substrates and endogenous or synthetic reductants, including glutathione (GSH), a thioredoxin reductase (TR)/thioredoxin (Trx)/NADPH reducing system, or tris (2-carboxyethyl) phosphine hydrochloride (TCEP). With either TR/Trx/NADPH or TCEP, wtAS3MT or AS3MT/M287T catalyzed conversion of iAs{sup III} to MAs{sup III}, methylarsonic acid (MAs{sup V}), dimethylarsinous acid (DMAs{sup III}), and dimethylarsinic acid (DMAs{sup V}); MAs{sup III} was converted to DMAs{sup III} and DMAs{sup V}. Although neither enzyme required GSH to support methylation of iAs{sup III} or MAs{sup III}, addition of 1 mM GSH decreased K{sub m} and increased V{sub max} estimates for either substrate in reaction mixtures containing TR/Trx/NADPH. Without GSH, V{sub max} and K{sub m} values were significantly lower for AS3MT/M287T than for wtAS3MT. In the presence of 1 mM GSH, significantly more DMAs{sup III} was produced from iAs{sup III} in reactions catalyzed by the M287T variant than in wtAS3MT-catalyzed reactions. Thus, 1 mM GSH modulates AS3MT activity, increasing both methylation rates and yield of DMAs{sup III}. AS3MT genotype exemplified by differences in regulation of wtAS3MT and AS3MT/M287T-catalyzed reactions by GSH may contribute to differences in the phenotype for arsenic methylation and, ultimately, to differences in the disease susceptibility in individuals chronically exposed to inorganic arsenic. -- Highlights: ► Human AS3MT and AS3MT(M287T) require a dithiol reductant for optimal activity. ► Both enzymes methylate arsenite to tri- and pentavalent methylated metabolites. ► Neither enzyme requires glutathione (GSH) to methylate arsenite or methylarsonite. ► However, in presence of a dithiol addition of 1 mM GSH increases methylation rates. ► In presence of 1 mM GSH, AS3MT(M287T) produces more dimethylarsinite than AS3MT.

60 APPLIED LIFE SCIENCES↗
NASA NTRS2004

Characterization of Ceramic Matrix Composite Vane Subelements Subjected to Rig Testing in a Gas Turbine Environment

Vane subelements were fabricated from a silicon carbide fiber-reinforced silicon carbide matrix (SiC/SiC) composite. A cross-sectional slice of an aircraft engine metal vane was the basis of the vane subelement geometry. To fabricate the small radius of the vane's trailing edge using stiff Sylramic SiC fibers, a unique SiC fiber architecture was developed. A test configuration for the vanes in a high pressure gas turbine environment was designed and fabricated. Testing was conducted using a pressure of 6 atm and combustion flow rate of 0.5 kg/sec, and consisted of fifty hours of steady state operation followed by 102 2-minute thermal cycles. A surface temperature of 1320 C was obtained for the EBC-coated SiC/SiC vane subelement. This paper will briefly discuss the vane fabrication, test configuration, and results of the vane testing. The emphasis of the paper is on characterization of the post-test condition of the vanes.

Verrilli, Michael↗
NASA NTRS2004

Probabilistic Residual Strength Model Developed for Life Prediction of Ceramic Matrix Composites

For the next generation of reusable launch vehicles, NASA is investigating introducing ceramic matrix composites (CMCs) in place of current superalloys for structural propulsion applications (e.g., nozzles, vanes, combustors, and heat exchangers). The higher use temperatures of CMCs will reduce vehicle weight by eliminating and/or reducing cooling system requirements. The increased strength-to-weight ratio of CMCs relative to superalloys further enhances their weight savings potential. However, in order to provide safe designs for components made of these new materials, a comprehensive life prediction methodology for CMC structures needs to be developed. A robust methodology for lifing composite structures has yet to be adopted by the engineering community. Current industry design practice continues to utilize deterministic empirically based models borrowed from metals design for predicting material life capabilities. The deterministic nature of these models inadequately addresses the stochastic character of brittle composites, and their empirical reliance makes predictions beyond the experimental test conditions a risky extrapolation. A team of engineers at the NASA Glenn Research Center has been developing a new life prediction engineering model. The Probabilistic Residual Strength (PRS) model uses the residual strength of the composite as its damage metric. Expected life and material strength are both considered probabilistically to account for the observed stochastic material response. Extensive experimental testing has been carried out on C/SiC (a candidate aerospace CMC material system) in a controlled 1000 ppm O2/argon environment at elevated temperatures of 800 and 1200 C. The test matrix was established to allow observation of the material behavior, characterization of the model, and validation of the model's predictive capabilities. Sample results of the validation study are illustrated in the graphs.

Thomas, David J.↗
NASA NTRS2004

Ceramic Matrix Composite Vane Subelement Testing in a Gas Turbine Environment

Vane subelements were fabricated from a silicon carbide fiber reinforced silicon carbide matrix (SiC/SiC) composite and were coated with an environmental barrier coating (EBC). A test configuration for the vanes in a gas turbine environment was designed and fabricated. Prior to testing, finite element analyses were performed to predict the temperatures and stress conditions present in vane during rig testing. This paper discusses the test configuration, the finite element analysis predictions, and results of the vane testing.

Verrilli, Michael↗
NASA NTRS2003

C/sic Life Prediction for Propulsion Applications

Accurate life prediction is critical to successful use of ceramic matrix composites (CMCs). The tools to accomplish this are immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for many reusable and single mission launch vehicle propulsion and airframe applications. This paper describes an approach and progress made to satisfy the need to develop an integrated life prediction system that addresses mechanical durability and environmental degradation of C/SiC.

Levine, Stanley R.↗
NASA NTRS2003

Ceramic Matrix Composites (CMC) Life Prediction Development - 2003

Accurate life prediction is critical to successful use of ceramic matrix composites (CMCs). The tools to accomplish this are immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for many reusable and single mission launch vehicle propulsion and airframe applications. This paper describes an approach and progress made to satisfy the need to develop an integrated life prediction system that addresses mechanical durability and environmental degradation of C/SiC.

Levine, Stanley R.↗
NASA NTRS2002

C/sic Life Prediction for Propulsion Applications

Accurate life prediction is critical to successful use of ceramic matrix composites (CMC). The tools to accomplish this are immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for many reusable and single mission launch vehicle propulsion and airframe applications. This paper describes an approach and process made to satisfy the need to develop an integrated life prediction system that addresses mechanical durability and environmental degradation of C/SiC. Issues such as oxidation, steam and hydrogen effects on material behavior are discussed. Preliminary tests indicate that steam will aggressively remove SiC seal coat and matrix in line with past experience. The kinetics of water vapor reaction with carbon fibers is negligible at 600 C, but comparable to air attack at 1200 C. The mitigating effect of steam observed in fiber oxidation studies has also been observed in stress rupture tests. Detailed microscopy of oxidized specimens is being carried out to develop the oxidation model. Carbon oxidation kinetics are reaction controlled at intermediate temperatures and diffusion controlled at high temperatures (approximately 1000 C). Activation energies for T-300 and interface pyrolytic carbon were determined as key inputs to the oxidation model. Crack opening as a function of temperature and stress was calculated. Mechanical property tests to develop and verify the probabilistic life model are very encouraging except for residual strength prediction. Gage width is a key variable governing edge oxidation of seal coated specimens. Future efforts will include architectural effects, enhanced coatings, biaxial tests, and LCF. Modeling will need to account for combined effects.

Levine, Stanley R.↗
NASA NTRS2002

C/SIC Life Prediction for Propulsion Applications

Accurate life prediction is critical to successful use of ceramic matrix composites (CMC). The tools to accomplish this are immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for many reusable and single mission launch vehicle propulsion and airframe applications. This paper describes an approach and progress made to satisfy the need to develop an integrated life prediction system that addresses mechanical durability and environmental degradation of C/SiC. Issues such as oxidation, steam and hydrogen effects on material behavior are discussed. Preliminary tests indicate that stream will aggressively remove SiC seal coat and matrix in line with past experience. The kinetics of water vapor reaction with carbon fibers is negligible at 600 C, but comparable to air attack at 1200 C. The mitigating effect of steam observed in fiber oxidation studies has also been observed in stress rupture tests. Detailed microscopy of oxidized specimens is being carried out to develop the oxidation model. Carbon oxidation kinetics are reaction controlled at intermediate temperatures and diffusion controlled at high temperatures (approx. 1000 C). Activation energies for T-300 and interface pyrolytic carbon were determined as key inputs to the oxidation model. Crack opening as a function of temperature and stress was calculated. Mechanical property tests to develop and verify the probabilistic life model are very encouraging except for residual strength prediction. Gage width is a key variable governing edge oxidation of seal coated specimens. Future efforts will include architectural effects, enhanced coatings, biaxial tests, and LCF. Modeling will need to account for combined effects.

Levine, Stanley R.↗
NASA NTRS2002

Design and Analysis of UHTC Leading Edge Attachment

NASA Glenn Research Center was contacted to provide technical support to NASA Ames Research Center in the design and analysis of an ultra high temperature ceramic (UHTC) leading edge. UHTC materials are being considered for reusable launch vehicles because their high temperature capability may allow for un-cooled sharp leading edge designs. While ceramic materials have the design benefit of allowing subcomponents to run hot, they also provide a design challenge in that they invariably must be in contact with cooler subcomponents elsewhere in the structure. NASA Glenn Research Center proposed a modification to an existing attachment design. Thermal and structural analyses of the leading edge assembly were carried out using ABAQUS finite element software. Final results showed that the proposed modifications aided in thermally isolating hot and cold subcomponents and reducing bearing stresses at the attachment location.

Thomas, David J.↗
NASA NTRS2000

Ceramic Matrix Composites (CMC) Life Prediction Method Development

Advanced launch systems (e.g., Reusable Launch Vehicle and other Shuttle Class concepts, Rocket-Based Combine Cycle, etc.), and interplanetary vehicles will very likely incorporate fiber reinforced ceramic matrix composites (CMC) in critical propulsion components. The use of CMC is highly desirable to save weight, to improve reuse capability, and to increase performance. CMC candidate applications are mission and cycle dependent and may include turbopump rotors, housings, combustors, nozzle injectors, exit cones or ramps, and throats. For reusable and single mission uses, accurate prediction of life is critical to mission success. The tools to accomplish life prediction are very immature and not oriented toward the behavior of carbon fiber reinforced silicon carbide (C/SiC), the primary system of interest for a variety of space propulsion applications. This paper describes an approach to satisfy the need to develop an integrated life prediction system for CMC that addresses mechanical durability due to cyclic and steady thermomechanical loads, and takes into account the impact of environmental degradation.

Levine, Stanley R.↗