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At least 37 records · Page 2

Helium concentration in the earth's lower atmosphere

A helium content of 5.222 + or - 0.017 ppm by volume has been established by measurements during 1981 of the earth's lower atmosphere, using isotope dilution mass spectrometry. This compares well with the currently accepted value of 5.239 + or - 0.004 ppm determined by Gluekhauf (1946) on the basis of measurements conducted in the 1930s. While processes that could have altered helium concentrations since the 1930s imply a significant increase in concentration, due to helium release during natural gas production, possible net helium losses from the atmosphere are not easily quantifiable.

Oliver, B. M.↗

Assessment of Amine-Based CO2BOLs for Direct Air Capture

Direct air capture (DAC) technologies extract CO 2 from the atmosphere for CO 2 storage, or utilization. Capturing CO 2 from the air is the most expensive application of carbon capture because CO 2 in the atmosphere is very dilute. There are limited number of CO 2 capture technologies for DAC application. This project aims at developing an energy efficient technology for DAC, leveraging two PNNL’s chemistries (solid and liquid CO 2 capture). Three CO 2 capture sorbents consisting of amine based CO 2 BOLs immobilized in mesoporous silica were designed, synthesized, and tested. These sorbents had ~ 19-23 wt.% amine loadings which is lower than typical amine-based silica sorbents. The surface area and pore volumes of these solid supported CO 2 BOLs are lower compared to those of the pristine silica support. The CO 2 capture performance of these materials was significantly lower than the typical silica supported amines due to low amine loading and higher molecular weight with low amine density. These results show that immobilize CO 2 BOLs in silica are not viable materials for removing CO 2 from ambient air. This project also designed, synthesized at tested liquid solvents for DAC application. Solvent properties that is vapor pressure, CO 2 uptake capacity, kinetics, and viscosity for three novel solvents were evaluated. The CO 2 uptake capacity for one of the most promising amine-based solvent BEPBEGDA was the highest at 13.2 wt% corresponding to 97 mol%. The vapor pressure of the BEPBEGDA solvents were very low at 80 °C compared to other solvents making them suitable for DAC application. The effect of humidity on the CO 2 capture performance of these solvents was evaluated which shows that presence of moisture doesn’t have a negative effect on the CO 2 uptake performance but makes it slightly better. The performances of these solvents were slightly below that of the 0.1M NaOH solution tested under similar conditions. Despite of the slightly lower CO 2 uptake, it is expected that these liquid solvents will have lower regeneration temperature and minimum evaporative losses due their low vapor pressure. Future work will focus on optimization of the liquid solvents for DAC application to improve both CO 2 capture efficiency and capacity without viscosity and vapor pressure increase. Testing of these solvents under DAC conditions using a gas liquid contactor that mimic industrial applications is needed. Solvent cost projection, techno-economic analysis and life cycle analysis are required to evaluate economic viability of this technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design, Fabrication, and testing of Direct Air Capture Sorbent modules to increase understanding of trade-offs in pressure drop and capture efficiency

Conference presentation for the work entitled “Design, Fabrication, and testing of Direct Air Capture Sorbent modules to increase understanding of trade-offs in pressure drop and capture efficiency”. In recent years, there has been a growing interest in Direct Air Capture (DAC) of CO2. This technology is gaining attention as a method to enhance the reduction of atmospheric greenhouse gases (GHGs), particularly when used alongside other decarbonization strategies. The route for efficient and net carbon negative DAC is challenging because CO2 in the atmosphere is highly diluted (~400ppm). This work, utilizing 3D printing capabilities for rapid prototyping, presents application-based findings on the design, fabrication, and testing of DAC module form factors that house solid sorbents. The work leverages an experimental rig that can achieve air throughput and velocities approaching that which are anticipated for commercial scales. The tradeoffs of pressure drop, footprint and capture efficiency are discussed for different orientations of a NETL patented sorbent material.

Riley, Jarrett↗

Air pollution from future giant jetports

Because aircraft arrive and depart in a generally upwind direction, the pollutants are deposited in a narrow corridor extending downwind of the airport. Vertical mixing in the turbulent atmosphere will not dilute such a trail, since the pollutants are distributed vertically during the landing and take-off operations. As a consequence, airport pollution may persist twenty to forty miles downwind without much attenuation. Based on this simple meteorological model, calculations of the ambient levels of nitric oxide and particulates to be expected downwind of a giant jetport show them to be about equal to those in present urban environments. These calculations are based on measured emission rates from jet engines and estimates of aircraft performance and traffic for future jetports.

Fay, J. A.↗

Sulfur dioxide and particles in quiescent volcanic plumes from Poas, Arenal, and Colima volcanos, Costa Rica and Mexico

Measurements of SO2 emission rates and concentrations and of particle distribution, size, shape, and composition were made in quiescent volcanic plumes emitted into the troposphere from Poas and Arenal volcanos, Costa Rica, and Colima volcano, Mexico. SO2 emission rates were 700 + or - 180 metric tons per day (t/d) for Poas, 210 + or - 30 t/d for Arenal, and 320 + or - 50 t/d for Colima. The concentrations of SO2 calculated from the COSPEC/lidar data were 5-380 ppb. Concentrations of SO2 measured directly by flame photometry were 10-250 ppb. Particles collected in the plumes with a quartz crystal microbalance impactor were mostly less than 3 microns in diameter and consisted of droplets of dilute sulfur-bearing solutions and minor amounts of layer silicate particles coated with a sulfur-bearing film or crust. Total particle concentrations were 4.7 micrograms per cu.m for Poas and 18.8 micrograms per cu.m for Colima. Comparison of concentrations of SO2 in the plumes with gas samples collected at fumaroles on the ground suggests that the plumes are diluted by the atmosphere by factors of up to 100,000.

Casadevall, T. J.↗

Nucleation of soot: experimental assessment of the role of polycyclic aromatic hydrocarbon (PAH) dimers

The irreversible dimerization of polycyclic aromatic hydrocarbons (PAHs) – typically pyrene (C 16 H 10 ) dimerization – is widely used in combustion chemistry models to describe the soot particle inception step. This study concerns itself with the detection and identification of dimers of flame-synthesized PAH radicals and closed-shell molecules and an experimental assessment of the role of these PAH dimers for the nucleation of soot. To this end, flame-generated species were extracted from an inverse co-flow flame of ethylene at atmospheric pressure and immediately diluted with excess nitrogen before the mixture was analyzed using flame-sampling tandem mass spectrometry with collision-induced fragmentation. Signal at m/z = 404.157 (C 32 H 20 ) and m/z = 452.157 (C 36 H 20 ) were detected and identified as dimers of closed-shell C 16 H 10 and C 18 H 10 monomers, respectively. A complex between a C 13 H 9 radical and a C 24 H 12 closed-shell PAH was observed at m/z = 465.164 (C 37 H 21 ). However, a rigorous analysis of the flame-sampled mass spectra as a function of the dilution ratio, defined as the ratio of the flow rates of the diluent nitrogen to the sampled gases, indicates that the observed dimers are not flame-born, but are produced in the sampling line. In agreement with theoretical considerations, this paper provides experimental evidence that pyrene dimers cannot be a key intermediate in particle inception at elevated flame temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The case for a Martian origin of the shergottites - Nitrogen and noble gases in EETA 79001

Nitrogen and noble gases have been measured in samples of a glass inclusion and its surrounding basaltic matrix in an Antarctic shergottite meteorite (EETA 79001). The nitrogen component was found trapped in the glass, but not the matrix, having a value of delta 15-N = +190 per mil. Ratios between abundances of Ar-40 and N-14, N-15 and N-14 in the glass are consistent with the dilution of a Martian atmospheric component. The trapped noble gases in the glass are similar to elemental and isotopic compositions measured in Mars atmosphere by the Viking lander, and are in general agreement with previous measurements. It is suggested that a sample of Martian atmosphere has been caught in the EETA 79001 glass, and that other shergottite, nakhilite, and chassignite meteorites with similar features probably also originated on Mars. A table is presented which lists the abundances of nitrogen and the noble gases found in the non-glassy matrix and in the EETA 79001 glass.

Becker, R. H.↗

Oxygen Isotope Fractionation in U 3 O 8 during Thermal Processing in Humid Atmospheres

The incorporation of oxygen isotopes from water into uranium oxides during industrial processing presents a pathway for determining a material’s geographical origin. This study is founded on the hypothesis that oxygen isotopes from atmospheric water vapor will exchange with isotopes of oxygen in solid uranium oxides during thermal processing or calcination. Using a commonly encountered oxide, U 3 O 8 , the exchange kinetics and equilibrium fractionation with water vapor (in a concentration range of 50–55% relative humidity) were investigated using processing temperatures of 400, 600, and 800 °C. In an atmosphere containing only water vapor diluted in N 2 , oxygen isotope equilibration in U 3 O 8 occurred within 12 h at 400 °C and within 2 h at 600 and 800 °C. Fractionation factors (1000lnα, U 3 O 8 –H 2 O) between the water and oxide were –12.1, –11.0, and –8.0 at 400, 600, and 800 °C, respectively. With both humidity and O 2 present in the calcining atmosphere, isotopic equilibration is attained within 2 h at and above 400 °C. In this mixed atmosphere, which was designed to emulate Earth’s troposphere, isotopes are incorporated preferentially from water vapor at 400 °C and from O 2 at 600 and 800 °C. Rapid and temperature/species-dependent isotope exchange also elucidated the impact of retrograde exchange in humid air, showing a shift from O 2 -dependent to H 2 O-dependent fractionation as U 3 O 8 cooled from 800 °C. These results confirm that uranium oxides inherit oxygen isotopes from humidity during thermal processing, illuminating an important mechanism in the formation of this forensic signature.

07 ISOTOPE AND RADIATION SOURCES↗

Structure–Transport Relationships of Water–Organic Solvent Co-transport in Carbon Molecular Sieve (CMS) Membranes

We explore the effects of the carbon molecular sieve (CMS) microstructure on the separation performance and transport mechanism of water–organic mixtures. Specifically, we utilize PIM-1 dense films and integrally skinned asymmetric hollow fiber membranes as polymer precursors for the CMS materials. The PIM-1 membranes were pyrolyzed under several different pyrolysis atmospheres (argon, carbon dioxide, and diluted hydrogen gas) and at multiple pyrolysis temperatures. Detailed gas physisorption measurements reveal that membranes pyrolyzed under 4% H 2 and CO 2 had broadened ultramicropore distributions (pore diameter <7 Å) compared to Ar pyrolysis, and pyrolysis under CO 2 increased ultramicropore volume and broadened micropore distributions at increased pyrolysis temperatures. Gravimetric water and p-xylene sorption and diffusion measurements reveal that the PIM-1-derived CMS materials are more hydrophilic than other CMS materials that have been previously studied, which leads to sorption-diffusion estimations showing water-selective permeation. Water permeation in the vapor phase, pervaporation, and liquid-phase hydraulic permeation reveal that the isobaric permeation modes (vapor permeation and pervaporation) are reasonably well predicted by the sorption-diffusion model, whereas the hydraulic permeation mode is significantly underpredicted (>250×). Conversely, the permeation of p-xylene is well predicted by the sorption-diffusion model in all cases. The collection of pore size analysis, vapor sorption and diffusion, and permeation in different modalities creates a picture of a combined transport mechanism in which water–under high transmembrane pressures–permeates via a Poiseuille-style mechanism, whereas p-xylene solutes in the mixture permeate via sorption-diffusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First-flight escape from spheres with R(-2) density distribution

Energy-independent first-flight transport kernels are evaluated for a spherical region with an R(-2) density distribution. The uncollided angular-flux distribution is obtained and integrated for a source distribution that is proportional to the density to give the uncollided emitted particle flux and current density. These are useful for the calculation of mass, energy, and momentum carried away by fast particles born in the medium. The data are relevant to estimate escape from weakly bound atmospheres such as comet comae, dilute circumstellar envelopes, and some unconfined laboratory plasmas.

Huebner, W. F.↗

A Study of Low-Temperature Neutron Star Atmospheres

We present a study of how a low-temperature accreted atmosphere influences the emitted X-ray spectrum of a neutron star. The atmosphere models and spectra were computed with Zcode, a multigroup radiation transfer code developed at the Los Alamos National Laboratory. Though the underlying hot neutron star behaves as a blackbody, the atmosphere shifts the peak of spectrum away from a blackbody and toward higher energies, producing an emitted spectrum similar to a dilute blackbody. Quantifying the effects of this atmosphere will remove a source of uncertainty in X-ray observations and better constrain the mass-radius relation for neutron stars and thus the equation of state of dense matter. We present a suite of these atmospheres with varying compositions and temperatures as well as the resulting spectra.

79 ASTRONOMY AND ASTROPHYSICS↗

Cumulonimbus Clouds Convert a Smaller Fraction of CAPE into Kinetic Energy in a Warmer Atmosphere

Abstract This study investigates how entrainment’s diluting effect on cumulonimbus updraft buoyancy is affected by the temperature of the troposphere, which is expected to increase by the end of the century. A parcel model framework is constructed that allows for independent variations in the temperature ( T ), the entrainment rate ε , the free-tropospheric relative humidity (RH), and the convective available potential energy (CAPE). Using this framework, dilution of buoyancy is evaluated with T and RH independently varied and with CAPE either held constant or increased with temperature. When CAPE is held constant, buoyancy decreases as T increases, with parcels in warmer environments realizing substantially smaller fractions of their CAPE as kinetic energy (KE). This occurs because the increased moisture difference between an updraft and its surroundings at warmer temperatures drives greater updraft dilution. Similar results are found in midlatitude and tropical conditions when CAPE is increased with temperature. With the expected 6%–7% increase in CAPE per kelvin of warming, KE only increases at 2%–4% K −1 in narrow updrafts but tracks more closely with CAPE at 4%–6% in wider updrafts. Interestingly, the rate of increase in the KE with T becomes larger than that of CAPE when the later quantity increases at more than 10% K −1 . These findings emphasize the importance of considering entrainment in studies of moist convection’s response to climate change, as the entrainment-driven dilution of buoyancy may partially counteract the influence of increases in CAPE on updraft intensity. Significance Statement Cumulonimbus clouds mix air with their surrounding environment through a process called entrainment, which controls how efficiently environmental energy is converted into upward speed in thunderstorm updrafts. Our research shows that warmer temperatures will exacerbate the moisture difference between cumulonimbus updrafts and their surroundings, leading to greater mixing and less efficient conversion of environmental energy into updraft speeds. This effect should be considered in future research that investigates how climate change will affect cumulonimbus clouds.

Peters, John M.↗

Mars volatile evolution - Evidence from stable isotopes

In the most strongly favored of the scenarios presently considered for Martian atmospheric evolution, oxygen fractionation by escape into space is diluted by exchange by a nonatmospheric reservoir as polar ice-water deposits exchange with atmospheric water over geologic time. The exchange of oxygen between atmospheric CO2 and H2O may account for the fractionation observed between those two species. Observations and numerical modeling efforts that may test the present results are suggested.

Jakosky, Bruce M.↗

Unveiling the porosity effect of superbase ionic liquid-modified carbon sorbents in CO 2 capture from air

Direct air capture (DAC) of CO 2 represents one of the most promising technologies to achieve negative carbon emissions. In this work, the superbase ionic liquids (ILs)-modified carbon substrates were developed for DAC of CO 2 by harnessing the strong CO 2 binding capability of IL and the ordered porous channels of the carbon supports. Detailed porosity analysis revealed that the IL with an aromatic cation and an oxygenate anion preferred to fill the micropores, and a thin layer was created on the surface of the mesopores. Strong π-π interaction between the IL layer and the carbon surface was disclosed by wide-angle X-ray scattering (WAXS) analysis, leading to enhanced thermal stability of the IL phase. For the same lL coating amount, the DAC of CO 2 evaluation revealed that a larger mesopore size and pore volume in the carbon/IL composite materials led to higher CO 2 uptake capacity by exposing more active sites to integrate CO 2 from diluted sources. Further, the thermodynamic analysis confirmed the critical role of IL coating in providing strong chemisorption sites and significantly improved selectivity to enrich the diluted CO 2 from the air atmosphere. This work provides guidance on leveraging the scaffolds' surface properties and porosities of the scaffolds to optimize DAC of CO 2 behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Weathering Incongruence in Mountainous Mediterranean Climates Recorded by Stream Lithium Isotope Ratios

Lithium isotope ratios (δ 7 Li) of rivers are increasingly serving as a diagnostic of the balance between chemical and physical weathering contributions to overall landscape denudation rates. Here, we show that intermediate weathering intensities and highly enriched stream δ 7 Li values typically associated with lowland floodplains can also describe small upland watersheds subject to cool, wet climates. This behavior is revealed by stream δ 7 Li between +22.4 and +23.5‰ within a Critical Zone observatory located in the Cévennes region of southern France, where dilute stream solute concentrations and significant atmospheric deposition otherwise mask evidence of incongruence. The water-rock reaction pathways underlying this behavior are quantified through a multicomponent, isotope-enabled reactive transport model. Using geochemical characterization of soil profiles, bedrock, and long-term stream samples as constraints, we evolve the simulation from an initially unweathered granite to a steady state weathering profile which reflects the balance between (a) fluid infiltration and drainage and (b) bedrock uplift and soil erosion. Enriched stream δ 7 Li occurs because Li is strongly incorporated into actively precipitating secondary clay phases beyond what prior laboratory experiments have suggested. Chemical weathering incongruence is maintained despite relatively slow reaction rates and moderate clay accumulation due to a combination of two factors. First, reactive primary mineral phases persist across the weathering profile and effectively “shield” the secondary clays from resolubilization due to their greater solubility. Second, the clays accumulating in the near-surface profile are relatively mature weathering byproducts. These factors promote characteristically low total dissolved solute export from the catchment despite significant input of exogenous dust.

54 ENVIRONMENTAL SCIENCES↗

Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor

The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

Evaluation Studies↗

Dilution impacts on smoke aging: evidence in Biomass Burning Observation Project (BBOP) data

Abstract. Biomass burning emits vapors and aerosols into the atmosphere that can rapidly evolve as smoke plumes travel downwind and dilute, affecting climate- and health-relevant properties of the smoke. To date, theory has been unable to explain observed variability in smoke evolution. Here, we use observational data from the Biomass Burning Observation Project (BBOP) field campaign and show that initial smoke organic aerosol mass concentrations can help predict changes in smoke aerosol aging markers, number concentration, and number mean diameter between 40–262 nm. Because initial field measurements of plumes are generally >10 min downwind, smaller plumes will have already undergone substantial dilution relative to larger plumes and have lower concentrations of smoke species at these observations closest to the fire. The extent to which dilution has occurred prior to the first observation is not a directly measurable quantity. We show that initial observed plume concentrations can serve as a rough indicator of the extent of dilution prior to the first measurement, which impacts photochemistry, aerosol evaporation, and coagulation. Cores of plumes have higher concentrations than edges. By segregating the observed plumes into cores and edges, we find evidence that particle aging, evaporation, and coagulation occurred before the first measurement. We further find that on the plume edges, the organic aerosol is more oxygenated, while a marker for primary biomass burning aerosol emissions has decreased in relative abundance compared to the plume cores. Finally, we attempt to decouple the roles of the initial concentrations and physical age since emission by performing multivariate linear regression of various aerosol properties (composition, size) on these two factors.

54 ENVIRONMENTAL SCIENCES↗