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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Concentrations of organophosphate flame retardants and plasticizers in urine from young children in Queensland, Australia and associations with environmental and behavioural factors

Highlights: • Eight OPFRs and eleven metabolites were measured in the urine of Australian kids. • Age was positively associated with BBOEP and negatively associated with BCIPP. • Mouthing activities were associated with higher concentrations of TBOEP, and TPHP. • Children living with window AC units had higher concentrations of BCIPHIPP and DBP. In recent years, the production and usage volumes of organophosphate flame retardants (OPFRs) has increased substantially. Certain OPFRs are suspected reproductive toxins, carcinogenic, and neurotoxic. Insufficient information is available on human exposure pathways to these chemicals, particularly in Australia. We aim to assess the association between OPFR concentrations in the urine of children to environmental and behavioural risk factors. Concentrations of eight OPFRs and eleven metabolites were measured in the urine of 51 children, aged 3–29 months, in Southeast Queensland, Australia and compared to their behavioural and environmental risk factor data obtained by an online questionnaire. Of the 11 OPFR metabolites analysed, 55% were frequently detected in the majority (> 80%) of samples. The most frequently detected metabolite was bis(1,3-dichloroisopropyl) phosphate (BDCIPP) (detected in 100% of samples), followed by 1-hydroxy-2-propyl bis(1-chloro-2-propyl) phosphate (BCIPHIPP) (96%), diphenyl phosphate (DPHP) (94%) and bis(1-chloroisopropyl) phosphate (BCIPP) (86%). In multivariable modelling, age was positively associated with concentrations of bis(2-butoxyethyl) phosphate (BBOEP) and negatively associated with concentrations of BCIPP and BCIPHIPP. Other non-age related factors, including vacuuming frequency, hand-washing frequency and presence and number of some electrical appliances in the home were also associated with concentrations of OPFR metabolites.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Plutonium(IV) and (V) sorption to goethite at sub-femtomolar to micromolar concentrations: Redox transformations and surface precipitation

Here, Pu(IV) and Pu(V) sorption to goethite was investigated over a concentration range of 10 –15 –10 –5 M at pH 8. Experiments with initial Pu concentrations of 10 –15 – 10 –8 M produced linear Pu sorption isotherms, demonstrating that Pu sorption to goethite is not concentration-dependent across this concentration range. Equivalent Pu(IV) and Pu(V) sorption Kd values obtained at 1 and 2-week sampling time points indicated that Pu(V) is rapidly reduced to Pu(IV) on the goethite surface. Further, it suggested that Pu surface redox transformations are sufficiently rapid to achieve an equilibrium state within 1 week, regardless of the initial Pu oxidation state. At initial concentrations >10 –8 M, both Pu oxidation states exhibited deviations from linear sorption behavior and less Pu was adsorbed than at lower concentrations. NanoSIMS and HRTEM analysis of samples with initial Pu concentrations of 10 –8 – 10 –6 M indicated that Pu surface and/or bulk precipitation was likely responsible for this deviation. In 10 –6 M Pu(IV) and Pu(V) samples, HRTEM analysis showed the formation of a body centered cubic (bcc) Pu 4 O 7 structure on the goethite surface, confirming that reduction of Pu(V) had occurred on the mineral surface and that epitaxial distortion previously observed for Pu(IV) sorption occurs with Pu(V) as well.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Cations Enhance Hydride Transfer to Noncatalytic Metals in Concentrated Alkaline Electrolytes

Alkali metal cations are known to influence the kinetics of the hydrogen evolution reaction (HER), acting as either promoters or inhibitors to the rate-determining step depending on the metal surface, local pH, and cation concentration. Despite the importance of concentrated electrolytes for commercial electrochemical cells, the impact of cations on the HER in concentrated alkaline environments (>1 M) and in mixed cation systems remains poorly understood. Here, this study quantifies the HER kinetics at polycrystalline metal surfaces (Pt, Au, Cu, and Fe) and the equilibrium solvation environment in pure and mixed alkali metal hydroxide electrolytes at concentrations up to 3.0 M. Kinetic analyses of Au, Cu, and Fe revealed a positive cation-concentration-effect that was primarily driven by changes to the charge transfer coefficient. Multinuclear NMR spectroscopy examined the solvation of H 2 O/OH – species and the alkali cations as a function of (mixed) alkali cation concentration(s), and demonstrated rapid exchange between solvent, hydroxide, and solvated cations. Together, these findings support models where HER kinetics on noncatalytic metal surfaces in strongly alkaline conditions are primarily governed by the average polarization and polarizability of the metal/solution interface and that increasing cation activity continues to increase the transfer coefficient at metal-hydroxide concentrations up to 3.0 M. Electrolytes and additives which can outcompete weakly hydrated cations and disrupt the interfacial water structure are expected to suppress parasitic HER at electrodes for energy storage and electroplating.

Cations↗
DOE OSTI2018

Solution Properties and Practical Limits of Concentrated Electrolytes for Nonaqueous Redox Flow Batteries

Nonaqueous redox flow batteries (NRFBs) use energized organic fluids that contain redox active organic molecules (ROMs) and supporting electrolyte. Such all-organic electrolytes have wider electrochemical stability windows than the more familiar aqueous electrolytes, potentially allowing a higher energy density in the solutions of charged ROMs. As this energy density increases linearly with the concentration of the charge carriers, physicochemical properties of concentrated ROM solutions in both states of charge present considerable practical interest. For NRFBs to become competitive with other types of flow cells, the current techno-economic analyses favor highly concentrated solutions (>1 M) with high ionic conductivity (>5 mS/cm). It is not presently clear that such solutions can have the required dynamic properties. In this paper, we show that ion diffusivities and conductivities of ROM-containing electrolytes reach maxima around 0.5 M and decrease significantly at higher concentrations; realistic limits are established for variations of these parameters. Furthermore, using closed-shell analogues for open-shell charged ROMs, we show that reconstitution of highly concentrated fluids during electrochemical charging will have strong adverse effects on their properties, including an increase in viscosity and decrease in conductivity and ion diffusivity. Finally, given our results, it appears that the target concentrations of NRFB fluids need to be reconsidered in terms of concentration-dependent conductivity and viscosity.

25 ENERGY STORAGE↗
DOE OSTI2024

Influence of Concentration Gradients on Electroconvection at a Cation-Exchange Membrane Surface

Membrane-based systems, such as electrodialysis, play an important role in desalination and industrial separation processes. Electrodialysis uses alternating anion- and cation-exchange membranes with a perpendicular electric field to generate concentrated and diluate streams from a feed solution. It is known that under overlimiting current conditions, reduced charge and mass transfer at the membrane interface leads to regions of high ion depletion generating instability and vortices termed electroconvection. While electroconvective mixing is known to directly impact the separation efficiency of electrodialysis, the influence of ion concentration gradients across the membrane experienced in a functional electrodialysis system is not known. Here, we report the influence of ion concentration gradients across a cation exchange membrane (Nafion) that is both aligned with and opposed to the applied electric field. Experiments were conducted by coflowing NaCl solutions of different concentrations (0.1–100 mM) on each side of the membrane, and electroconvection was visualized with a fluorescence dye (Rhodamine 6G). Here, we obtained concentration profiles from fluorescence image data and systematically measured the thickness of the depletion boundary layer d BL under different conditions. We found smaller d BL values at a higher flow rate both with and without concentration gradients. Our results show that electroconvection is enhanced when the electric field is opposite to the direction of the concentration gradient.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

EELS Studies of Cerium Electrolyte Reveal Substantial Solute Concentration Effects in Graphene Liquid Cells

Graphene liquid cell transmission electron microscopy is a powerful technique to visualize nanoscale dynamics and transformations at atomic resolution. However, the solution in liquid cells is known to be affected by radiolysis, and the stochastic formation of graphene liquid cells raises questions about the solution chemistry in individual pockets. In this study, electron energy loss spectroscopy (EELS) was used to evaluate a model encapsulated solution, aqueous CeCl 3 . First, the ratio between the O K-edge and Ce M-edge was used to approximate the concentration of cerium salt in the graphene liquid cell. It was determined that the ratio between oxygen and cerium was orders of magnitude lower than what is expected for a dilute solution, indicating that the encapsulated solution is highly concentrated. To probe how this affects the chemistry within graphene liquid cells, the oxidation of Ce 3+ was measured using time-resolved parallel EELS. Here, it was determined that Ce 3+ oxidizes faster under high electron fluxes, but reaches the same steady-state Ce 4+ concentration regardless of flux. The time-resolved concentration profiles enabled direct comparison to radiolysis models, which indicate rate constants and g-values of certain molecular species are substantially different in the highly concentrated environment. Finally, electron flux-dependent gold nanocrystal etching trajectories showed that gold nanocrystals etch faster at higher electron fluxes, correlating well with the Ce 3+ oxidation kinetics. Understanding the effects of the highly concentrated solution in graphene liquid cells will provide new insight on previous studies and may open up opportunities to systematically study systems in highly concentrated solutions at high resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Experimental Measurement of the Solid Particle Concentration in Geophysical Turbulent Gas-Particle Mixtures

Dilute gas-particle mixtures in which the particles are carried by the turbulent fluid are found in various geophysical contexts, from cold snow avalanches to hot pyroclastic density currents. Though previous studies suggest that such mixtures have maximum particle concentrations of a few volume percent, the dependence of this maximum concentration on the Reynolds number is unclear. We addressed this issue through laboratory experiments in a vertical pipe, where dilute gas-particle mixtures were created by injecting a turbulent air flow from below. Nearly monodisperse mixtures of glass beads of different grain sizes (77 to 1,550 μm) were used with varying bulk concentrations from 0.025 to 8 vol. %. To create quasi-static mixtures, the mean air velocity matched the terminal settling velocity for the grain sizes investigated. The maximum Reynolds numbers of the mixtures were ~104–106. The air pressure indicated full support of the particle weight at concentrations down to 0.025 vol. %. Above a critical particle concentration, at which all the particles were suspended, subsequent additional particles were not maintained in the mixture and led to the formation of clusters that settled downward in the pipe to form a dense fluidized bed. Maximum mean particle concentrations of the dilute mixtures increased from ~1 to ~2.8 vol. % and reached a plateau at increasing mixture Reynolds number. These results give insights into the maximum particle concentrations of geophysical turbulent gas-particle mixtures and may serve to constrain observations as well as the input and output data of models.

58 GEOSCIENCES↗
DOE OSTI2022

Diel mercury concentration variations in a mercury-impacted stream

Here, filtered and particulate mercury (Hg) and methylmercury (MMHg), and associated water chemistry parameters, were evaluated bi-hourly for several 30 h periods during the summer and winter seasons at several distinct locations (downstream forested, midstream urban/suburban, upstream industrial) along a creek contaminated with high levels of inorganic Hg to determine if biogeochemical Hg and MMHg cycles respond to the daily photocycle. In summer particulate Hg and MMHg concentrations doubled overnight (excluding the upstream industrial site) concurrent with increases in turbidity and total suspended sediment; no such pattern was evident in winter. Seasonal and diel changes in the activity of macrobiota affecting the suspension of contaminated sediments are likely responsible for these patterns as other potential explanatory variables (e.g., instrument drift, pH, discharge) could not account for the range and timing of our observations. Diel patterns in filtered Hg (Hg D ) were significant only at locations and times of the year when channel shading was not present and daytime concentrations increased 22–89% above nighttime minima likely caused by direct and indirect photochemical reactions. Relationships between Hg D and dissolved organic carbon (DOC) concentration or character were inconsistent between sites. Unlike Hg D , there were significant diel patterns in filtered MMHg (MMHg D ) at all sites and times of year, with summer concentrations peaking in mid to late afternoon while the timing differed in winter, with concentrations peaking after sunset. Daily variability in MMHg D concentration ranged between 25 and 75%. The results imply key controls on net methylation occur within the stream or on the stream bed and include factors such as small-scale temperature changes in the water column and photosynthetic activity of stream biofilm. With respect to stream monitoring, results from this study indicate (1) consistent timing in stream Hg and MMHg sampling is required for accurate assessment of long-term trends, (2) in situ measurements of turbidity can be used to quantify diel dynamics of both particulate Hg and MMHg concentrations, and (3) in situ fluorescing dissolved organic matter (FDOM), a potential proxy for DOC, was not capable of resolving diel dynamics of filtered Hg or MMHg.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

The effects of aluminum concentration on the microstructural and electrochemical properties of lithium lanthanum zirconium oxide

Cubic lithium lanthanum zirconium oxide (Li 7-x Al x La 3 Zr 2 O 12 , LLZO) garnet has gained attention as a promising next-generation electrolyte for lithium batteries due to its high ionic conductivity and chemical stability with lithium metal. The high conductivity can be achieved through doping over a range of aluminum concentrations. In this study, we hot-pressed samples to achieve <2% nominal porosity with aluminum concentrations from x = 0.25–0.55 mol to understand the effect of aluminum on microstructure and electrochemistry. It was observed that beyond the aluminum solubility limit (x = ~0.40), resistive secondary phases formed at the grain boundaries. As a result, the percent grain boundary resistance increased from 17.6 to 41.2% for x = 0.25 and x = 0.55, respectively. Both the grain boundary and bulk activation energies remained relatively constant as the aluminum concentrations increased (~0.44 eV and ~0.39 eV, respectively). It was, therefore, surmised that the mobility term of the Nernst–Einstein equation was roughly independent of aluminum concentration and the major variable controlling bulk conductivity was the number of lithium charge carriers. As a result, as the aluminum concentration increased from x = 0.25 to x = 0.55 the bulk conductivity decreased from 0.56 to 0.15 mS cm -1 . Following these trends of increasing grain boundary resistance and decreasing bulk conductivity with increasing aluminum concentration, x = 0.25 had the highest total conductivity (0.46 mS cm -1 ). We demonstrated that aluminum concentration has a significant effect on the microstructure and electrochemical properties of LLZO. In conclusion, we believe this work could help understand how to link processing, microstructure, and electrochemical properties to guide the manufacturing of LLZO for use in solid-state batteries.

25 ENERGY STORAGE↗
DOE OSTI2014

Si concentration dependence of structural inhomogeneities in Si-doped Al{sub x}Ga{sub 1−x}N/Al{sub y}Ga{sub 1−y}N multiple quantum well structures (x = 0.6) and its relationship with internal quantum efficiency

We investigated the distribution of luminescence in Si-doped Al{sub x}Ga{sub 1−x}N/Al{sub y}Ga{sub 1−y}N multiple quantum well (MQW) structures (x = 0.6) with different Si concentrations by cathodoluminescence (CL) mapping combined with scanning electron microscopy. The effects of surface morphology, dark spot density, and full width at half-maximum of spot CL spectra on internal quantum efficiency (IQE) were determined. A flat surface morphology and uniform CL map were observed for Si-doped AlGaN MQWs, in contrast to undoped AlGaN MQW and Si-doped AlGaN with relatively low Al content. The dark spot density in the Si-doped AlGaN MQWs increased exponentially as the Si concentration increased and did not explain the Si concentration dependence of IQE. In contrast, there was a clear correlation between the dark spot density and IQE of the AlGaN MQWs at a constant Si concentration. The emission energy distribution arising from the inhomogeneity of the relative Al content and the well layer thickness was estimated by monochromatic CL measurements, although there was almost no difference in the distribution for different Si concentrations. Therefore, the previously reported dependence of the defect complexes on Si concentration is reflected in the IQE of Si-doped AlGaN MQWs. Defect complexes composed of cation vacancies and impurities rather than dislocations and interfacial quality are the major contributor to the IQE of the Si-doped AlGaN MQWs with different Si concentrations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Constraining the mass-concentration relation through weak lensing peak function

Halo masses and concentrations have been studied extensively, by means of N-body simulations as well as observationally, during the last decade. Nevertheless, the exact form of the mass-concentration relation is still widely debated. One of the most promising method to estimate masses and concentrations relies on gravitational lensing from massive halos. Here we investigate the impact of the mass-concentration relation on halo peak abundance in weak lensing shear maps relying on the aperture mass method for peak detections. After providing a prescription to take into account the concentration dispersion (always neglected in previous works) in peak number counts predictions, we assess their power to constrain the mass-concentration relation by means of Fisher matrix technique. We find that, when combined with different cosmological probes, peak statistics information from near-future weak lensing surveys provides an interesting and complementary alternative method to lessen the long standing controversy about the mass-concentration relation.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2023

The impact of halo concentration on the Sunyaev Zel’dovich effect signal from massive galaxy clusters

ABSTRACT The Sunyaev Zel’dovich (SZ) effect is sensitive to the pressure of ionized gas inside galaxy clusters, which is in turn controlled largely by the gravitational potential of the cluster. Changing the concentration parameter describing the cluster mass distribution impacts the gravitational potential and thus the cluster SZ signal, with implications for cosmological and other analyses of SZ-selected clusters. We investigate the concentration–SZ relation in theory and simulations. We find that the impact of concentration on the inner SZ profile (R ≲ 0.75R200c) can be captured with standard polytropic gas models. However, we find that such models do a poor job of reproducing the outer SZ profiles (R ≳ 0.75R200c) and the relation between the integrated SZ signal, Y, and concentration. This disagreement results from a sharp truncation of the gas pressure profile near the splashback radius, likely caused by virial shocks. We develop a simple description of the truncation that leads to a good match with the simulated SZ profiles out to several R200c for clusters of varying mass and concentration, and that also accurately predicts the concentration–Y relationship. Finally, we determine how inference of the linear bias parameter and splashback radius for SZ-selected clusters can be biased by ignoring the concentration dependence of the SZ signal, finding that bias to the former is essentially negligible, while bias to the latter can be as much as 2 per cent.

Astronomy & Astrophysics↗
DOE OSTI2022

Variation in carbon and nitrogen concentrations among peatland categories at the global scale

Peatlands account for 15 to 30% of the world’s soil carbon (C) stock and are important controls over global nitrogen (N) cycles. However, C and N concentrations are known to vary among peatlands contributing to the uncertainty of global C inventories, but there are few global studies that relate peatland classification to peat chemistry. We analyzed 436 peat cores sampled in 24 countries across six continents and measured C, N, and organic matter (OM) content at three depths down to 70 cm. Sites were distinguished between northern (387) and tropical (49) peatlands and assigned to one of six distinct broadly recognized peatland categories that vary primarily along a pH gradient. Peat C and N concentrations, OM content, and C:N ratios differed significantly among peatland categories, but few differences in chemistry with depth were found within each category. Across all peatlands C and N concentrations in the 10–20 cm layer, were 440 ± 85.1 g kg -1 and 13.9 ± 7.4 g kg -1 , with an average C:N ratio of 30.1 ± 20.8. Among peatland categories, median C concentrations were highest in bogs, poor fens and tropical swamps (446–532 g kg -1 ) and lowest in intermediate and extremely rich fens (375–414 g kg -1 ). The C:OM ratio in peat was similar across most peatland categories, except in deeper samples from ombrotrophic tropical peat swamps that were higher than other peatlands categories. Peat N concentrations and C:N ratios varied approximately two-fold among peatland categories and N concentrations tended to be higher (and C:N lower) in intermediate fens compared with other peatland types. This study reports on a unique data set and demonstrates that differences in peat C and OM concentrations among broadly classified peatland categories are predictable, which can aid future studies that use land cover assessments to refine global peatland C and N stocks.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Modeling spatial patterns in soil arsenic to estimate natural baseline concentrations

ABSTRACT Arsenic in soil is an important public health concern. Toxicity guidelines and models based on laboratory studies (i.e., U.S. EPA’s Integrated Risk Information System) should consider natural soil As concentrations to avoid unnecessary remediation burdens on society. We used soil and stream sediment samples from the USGS National Geochemical Survey database to assess the spatial distribution of natural As in a 1.16E+5 km2 area. Samples were collected at 348 soil and 144 stream locations, providing approximately one sample for every 290 km2. Sample sites were selected to minimize the potential influence of anthropogenic inputs. Samples were processed using acid digestion of whole samples (concentrated HCl and ascorbic acid) and concentrations were measured using hydride-generation atomic absorption spectrometry. Soil As ranged from 2.0 to 45.6 mg kg-1. Geostatistical techniques were used to model and map the spatial variability of As. The mean and variance at unsampled locations were estimated using sequential Gaussian simulation. Five areas of elevated concentration (> the median of 10 mg kg-1) were identified and the relationships to geologic parent materials, glacial sedimentation patterns, and soil conditions interpreted. Our results showed As concentrations >10 mg kg-1 were common, and >20 mg kg-1 were not unusual for the central and west central portions of Ohio (USA). In contrast, concentrations <4 mg kg-1 were rare. Measured concentrations typically exceeded the soil As human generic screening levels of 0.39 mg/kg (1); the calculated value that corresponds to a cancer risk level of 1 in 1,000,000 for soil ingestion. Because the As content of Ohio soils is similar to many world soils, the USEPA generic soil screening level of 0.39 mg/kg is of little utility. A more useful and practical approach would be the uses of natural background levels. Regional soil As patterns based on geology and biogeochemistry and not political boundaries should be used for soil screening and other risk assessment determinations.

arsenic, background, mapping, geostatistics, toxic↗
DOE OSTI2016

Pollutant Concentrations and Emission Rates from Scripted Natural Gas Cooking Burner Use in Nine Northern California Homes

METHODS: Combustion pollutant concentrations were measured during the scripted operation of natural gas cooking burners in nine homes. In addition to a base condition of closed windows, no forced air unit (FAU) use, and no mechanical exhaust, additional experiments were conducted while operating an FAU and/or vented range hood. Test homes included a 26m2 two-room apartment, a 134m2 first floor flat, and seven detached homes of 117–226m2. There were four single-story, four two-story and one 1.5 story homes. Cooktop use entailed boiling and simmering activities, using water as a heat sink. Oven and broiler use also were simulated. Time-resolved concentrations of carbon dioxide (CO2), nitric oxide (NO), nitrogen oxides (NOX), nitrogen dioxide (NO2), particles with diameters of 6 nm or larger (PN), carbon monoxide (CO), and fine particulate matter (PM2.5) were measured in the kitchen (K) and bedroom area (BR) of each home. CO2, NO, NO2, and PN data from sequential experiments were analyzed to quantify the contribution of burner use to the highest 1h and 4h time-integrated concentrations in each room. RESULTS: Four of the nine homes had kitchen 1h NO2 exceed the national ambient air quality standard (100 ppb). Two other homes had 1h NO2 exceed 50 ppb in the kitchen, and three had 1h NO2 above 50 ppb in the bedroom, suggesting substantial exposures to anyone at home when burners are used for a single substantial event. In all homes, the highest 1h kitchen PN exceeded 2 x105 cm-3-h, and the highest 4h PN exceeded 3 x105 cm-3-hr in all homes. The lowest 1h kitchen/bedroom ratios were 1.3–2.1 for NO in the apartment and two open floor plan homes. The largest K/BR ratios of 1h NO2 were in a two-story 1990s home retrofitted for deep energy savings: ratios in this home were 3.3 to 6.6. Kitchen 1h ratios of NO, NO2 and PN to CO2 were used to calculate fuel normalized emission factors (ng J-1). Range hood use substantially reduced cooking burner pollutant concentrations both in the kitchen and bedroom of several homes. A hood with large capture volume and a measured flow of 108 L/s reduced concentrations 80-95%. IMPLICATIONS: These measurements demonstrate that operation of natural gas cooking burners without venting can cause short-term kitchen concentrations of NO2 to exceed the US outdoor health standard, and can elevate concentrations of NO, NO2, and ultrafine particles throughout the home. Results are generally consistent with a recent simulation study that estimated widespread 1h NO2 exposures exceeding 100 ppb in homes that use gas burners without venting. While operating a venting range hood can greatly reduce pollutant levels from burner use (and presumably from cooking as well), performance varies widely across hoods. Increased awareness of the need to ventilate when cooking would substantially reduce in-home exposure to NO2 and ultrafine particles in California homes. Helping consumers select effective hoods, for example by publishing capture efficiency performance ratings, also would help reduce exposure.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Validating Hydrogen Concentrations Ahead of Crack Tips

Current models for hydrogen embrittlement rely on adjustable parameters to correct for uncertainties in crack tip stress fields and subsequent H 2 -concentrations. Techniques are needed to quantify these concentrations ahead of crack tips in mechanically loaded materials, providing data for model calibration and validation. The goal of this work was to establish advanced analytical techniques to detect and quantitatively measure hydrogen ahead of cracks in stressed solids. Two advanced analytical techniques, kelvin probe force microscopy (KPFM) and nuclear reaction analysis (NRA), were explored to evaluate the feasibility to provide qualitative and quantitative H 2 -concentration fields in geometries designed to be 'loaded' while under observation. The feasibility of the KPFM technique at detecting hydrogen was evaluated using electrochemically precharged hydrogen as well as a mixed hydrogen gas atmosphere. The KPFM technique was able to detect the presence of elevated stress and hydrogen concentrations ahead of a tensile loaded crack tip. The results suggest that KPFM is a viable technique for qualitatively imaging changes in stress and hydrogen concentrations on the scale needed to inform predictive models. KPFM could be used to provide local stress and hydrogen variations associated with hydrogen traps or different phases which require sensitive measurements on the micron scale. NRA provided quantitative measurements of the hydrogen-isotope deuterium ahead of a tensile loaded notch, however, the vacancy formation due to the incident high energy He 3 beam overwhelmed stress-assisted enhancement of deuterium concentrations such that the effect of stress was overshadowed in this analysis. Modeling of the chemo- mechanical hydrogen concentration change was used to verify this observation.

08 HYDROGEN↗
DOE OSTI2020

Measurement of Argon-37 Background Concentrations in the Atmosphere

Radioisotopes of noble gases, primarily xenon and argon, are important indicators of underground nuclear explosions. The Comprehensive Nuclear-Test-Ban Treaty (CTBT) includes monitoring capabilities to identify potential nuclear explosions conducted in violation of the CTBT. This monitoring currently focuses on measurement of the xenon isotopes 133 Xe, 135 Xe, 131 mXe and 133 mXe. However, it is predicted that within 100 days of an underground nuclear explosion (UNE) 37 Ar would be released to the atmosphere at higher concentrations than xenon isotopes (Haas et al. 2010). Therefore, inclusion of 37 Ar measurement capabilities at atmospheric International Monitoring System (IMS) stations could improve the capability to detect a nuclear explosion. At an IMS station, it could be difficult to determine what constitutes an elevated concentration as a result of an UNE without first understanding the expected range of background concentrations. This work describes our analysis of atmospheric samples for 37 Ar to evaluate the range of background concentrations. The range of 37 Ar concentrations measured in atmospheric air samples was relatively narrow ranging between less than 1 mBq/m 3 to greater than 2 mBq/m 3 . The average atmospheric concentration of all samples was 0.98 mBq/m 3 , with a standard deviation of 0.5 mBq/m 3 . This is consistent with previous published results. The results presented here demonstrate the capability to detect background concentrations of 37 Ar in atmospheric air.

61 RADIATION PROTECTION AND DOSIMETRY↗
DOE OSTI2022

Effects of high concentrate rations on ruminal fermentation and microbiota of yaks

Ruminal microflora is closely correlated with the ruminant’s diet. However, information regarding the effect of high concentrate diets on rumen microflora in yaks is lacking. In the current study, 24 healthy male yaks were randomly assigned to two groups, each fed with different diets: less concentrate (LC; concentrate: coarse = 40: 60) and high concentrate (HC; concentrate: coarse = 80: 20) diets. Subsequently, a 21-day feeding trial was performed with the yaks, and rumen fluid samples were collected and compared using 16 s rRNA sequencing. The results showed that NH 3 -N, total VFA, acetate, butyrate, isobutyrate, and isovalerate were significantly higher in the HC group than that in the LC group ( p < 0.05), while microbial diversity and richness were significantly lower in the HC group ( p < 0.05). Principal coordinate analysis indicated that rumen microflora was significantly different in LC and HC groups ( p < 0.05). In the rumen, phyla Firmicutes and Bacteroidota were the most abundant bacteria, with Firmicutes being more abundant, and Bacteroidota being less abundant in the HC group than those found in the LC group. Christensenellaceae_R-7_group and Prevotella are the highest abundant ones at the genus level. The relative abundance of Acetitomaculum , Ruminococcus , and Candidatus_Saccharimonas were significantly higher in the HC group than that in the LC group ( p < 0.05), while the relative abundance of Olsenella was significantly lower in the HC group than in the LC group ( p < 0.05). Compared to the LC group, the relative abundance of Prevotella , Ruminococcus , and Candidatus_Saccharimonas was significantly higher in the HC group. The relative abundances of Prevotella , Prevotellaceae_UCG-003 , Olsenella , Ruminococcus , Acetitomaculum , Candidatus_Saccharimonas , and NK4A214_group were correlated with ruminal fermentation parameters ( p < 0.05). Furthermore, PICRUSt 2 estimation indicated that microbial genes associated with valine, leucine, and isoleucine biosynthesis were overexpressed in the rumen microflora of yaks in the HC group ( p < 0.05). Conclusively, our results suggest that high concentrate diets affect the microflora composition and fermentation function in yak rumen. The present findings would provide new insights into the health of yaks under high concentrate feeding conditions and serve as a potent reference for the short-term fattening processes of yaks.

Pang, Kaiyue↗