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At least 703 records · Page 39

Tropical Simultaneous Nadir Observations for IR Sounder Evaluation and Comparison

Simultaneous Nadir Observations (SNOs) contain thousands of pairs of observations taken within 8 km and 10 minutes. SNOs have been very useful for comparisons in polar conditions. But classic SNO pairing criteria have very low yield in the tropics, making these SNOs less useful for investigating instrument performance for hotter scenes or scenes with high contrast. We introduce a modified methodology, which finds pairs of matched spectra in a wider angular range but is restricted to the tropics. We illustrate this with AIRS and CrIS data. Insight into instrument differences is gained from statistical distributions of the residual differences between the matched pairs. A sample analysis compares AIRS and CrIS brightness temperature at 900 cm-1 as function of scene brightness temperature. The proposed method may be applicable to matchups of other sensors on different spacecraft.

AIRS↗

A Comprehensive Assessment of Biologicals Contained Within Commercial Airliner Cabin Air

Both culture-based and culture-independent, biomarker-targeted microbial enumeration and identification technologies were employed to estimate total microbial and viral burden and diversity within the cabin air of commercial airliners. Samples from each of twenty flights spanning three commercial carriers were collected via air-impingement. When the total viable microbial population was estimated by assaying relative concentrations of the universal energy carrier ATP, values ranged from below detection limits (BDL) to 4.1 x 106 cells/cubic m of air. The total viable microbial population was extremely low in both of Airline A (approximately 10% samples) and C (approximately 18% samples) compared to the samples collected aboard flights on Airline A and B (approximately 70% samples). When samples were collected as a function of time over the course of flights, a gradual accumulation of microbes was observed from the time of passenger boarding through mid-flight, followed by a sharp decline in microbial abundance and viability from the initiation of descent through landing. It is concluded in this study that only 10% of the viable microbes of the cabin air were cultivable and suggested a need to employ state-of-the art molecular assay that measures both cultivable and viable-but-non-cultivable microbes. Among the cultivable bacteria, colonies of Acinetobacter sp. were by far the most profuse in Phase I, and Gram-positive bacteria of the genera Staphylococcus and Bacillus were the most abundant during Phase II. The isolation of the human pathogens Acinetobacter johnsonii, A. calcoaceticus, Janibacter melonis, Microbacterium trichotecenolyticum, Massilia timonae, Staphylococcus saprophyticus, Corynebacterium lipophiloflavum is concerning, as these bacteria can cause meningitis, septicemia, and a handful of sometimes fatal diseases and infections. Molecular microbial community analyses exhibited presence of the alpha-, beta-, gamma-, and delta- proteobacteria, as well as Gram-positive bacteria, Fusobacteria, Cyanobacteria, Deinococci, Bacterioidetes, Spirochetes, and Planctomyces in varying abundance. Neisseria meningitidis rDNA sequences were retrieved in great abundance from Airline A followed by Streptococcus oralis/mitis sequences. Pseudomonas synxantha sequences dominated Airline B clone libraries, followed by those of N. meningitidis and S. oralis/mitis. In Phase II, Airline C, sequences representative of more than 113 species, enveloping 12 classes of bacteria, were retrieved. Proteobacterial sequences were retrieved in greatest frequency (58% of all clone sequences), followed in short order by those stemming from Gram-positives bacteria (31% of all clone sequences). As for overall phylogenetic breadth, Gram-positive and alpha-proteobacteria seem to have a higher affinity for international flights, whereas beta-and gamma-proteobacteria are far more common about domestic cabin air parcels in Airline C samples. Ultimately, the majority of microbial species circulating throughout the cabin airs of commercial airliners are commensal, infrequently pathogenic normal flora of the human nasopharynx and respiratory system. Many of these microbes likely originate from the oral and nasal cavities, and lungs of passengers and flight crew and are disseminated unknowingly via routine conversation, coughing, sneezing, and stochastic passing of fomites. The data documented in this study will be useful to generate a baseline microbial population database and can be utilized to develop biosensor instrumentation for monitoring microbial quality of cabin or urban air.

microbial diversity↗

Air-, N2-, and O2-broadening and shift coefficients in the nu(3) spectral region of (C-12)H4

Results are presented of an analysis of 29 room-temperature laboratory absorption spectra of a dilute CH4 sample in dry air, N2, and O2 at total pressures ranging from 60 to 550 torr, yielding values of pressure-broadening and pressure-induced-shift coefficients for more than 450 vibration-rotation transitions in the nu(3), nu(2) + nu(4), and 2nu(2)-super-2 bands of (C-12)H4. Comparisons of the present results for the nu(3) and nu(2) + nu(4) bands with previous measurements on other bands and isotopes of CH4 show that, for a given transition, broadening by air and N2 are nearly equal, and broadening by O2 is smaller by less than 10 percent. It is also found that the pressure shift coefficients are more vibrational dependent than the pressure broadening coefficients.

Benner, D. C.↗

Assessment of the 3420 Building Filtered Exhaust Stack Sampling Probe Location: Stack Verification Following Fan and Air Blender Additions

The Pacific Northwest National Laboratory (PNNL) 3420 Building, which is part of the Physical Sciences Facility (PSF), houses radiological capabilities that results in the requirement that emissions monitoring must be conducted for potential radionuclides in the exhaust air discharge of this building. The air monitoring system is required to conform to Title 40 of the Code of Federal Regulations part 61 (40 CFR 61) Subpart H, which in turns requires a sampling probe in the exhaust stream to conform to the criteria of American National Standards Institute / Health Physics Society (ANSI/HPS) N13.1-2011, Sampling and Monitoring Releases of Airborne Radioactive Substances from the Stack and Ducts of Nuclear Facilities. To support the air emissions permit for the 3420 Building on the PNNL campus, stack testing that used computational fluid dynamics (CFD) modeling as a surrogate stack and verification tests of velocity uniformity and flow angle on the retrofitted facility stack was performed. The ANSI/HPS N13.1-2011 criteria for the air monitoring probe location are that velocity uniformity, gaseous tracer uniformity, and particulate tracer uniformity must be less than or equal to 20%COV. Furthermore, no point in the sampling location may have a gaseous tracer concentration that varies from the mean concentration by more than 30%. Additionally, the flow angle at the sampling location must not be more than 20°. The CFD modeling of the stack, as reported by Recknagle et al. (2018) demonstrated that the stack meets the criteria at the probe location. The velocity uniformity and flow angle results from the 3420 stack verification tests, performed in October 2020, demonstrated that the CFD model results may be used to support the qualification of the stack sampling location. The measured velocity uniformity verification test result was 1.4%COV. This value is well within the uniformity criterion, which is that the velocity uniformity be =20%COV. Additionally, this value is well within the criterion that the actual stack measurement must be within 5% of the surrogate stack result of 2.1%COV when all four fans were operating. Additionally, the measured average flow angle at the 3420 stack monitor location was 15.5 degrees. Although this is higher than expected based on the CFD model, the result is =20 degrees, so the criterion is met. Based on these stack verification test results, the reconfigured 3420 Building filtered exhaust stack meets the qualification criteria given in the ANSI/HPS N13.1-2011 standard. Further changes to the system configuration or operating conditions that are outside the bounds described in this and the CFD report (Recknagle et al., 2018) may require additional tests and additional analysis to determine compliance with the standard.

3420 Building↗

Consequence Assessment of the WIPP Radiological Release from February 2014

We report on 14 February 2014, a continuous air monitor (CAM) alarm at the exit of panel 7 in the Waste Isolation Pilot Plant (WIPP) underground facility caused the mine ventilation to shift from unfiltered air over to HEPA filtration for its effluent. Subsequent measurements of the effluent at both pre- and post-HEPA filtration using representative sampling demonstrated that a release had occurred. Using modeling based on measured effluent activity, onsite dose estimates were calculated and later measured via bioassay to be less than 0,1 mSv from intakes of radioactivity. Lastly, the maximum offsite dose potential to nearby dwellings was modeled to be 1 µSv or less, which was consistent with air samples being taken at those dwellings during the release, demonstrating impressive accuracy and precision. No worker or public dose limits have been exceeded, and the release was substantially below the annual release limits for the WIPP site.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Batch Gas-Sampling System

Sampler collects air or other gases in consistent way and stabilizes them for later chemical analysis. Device used for concentrations ranging from few parts per million to 100 percent. Also separates and collects particles in gas for analysis. Gas flows into vacuum sphere when solenoid valve opened. As it passes through conversion tube, constituent of gas forms stable compound that remains in conversion tube for analysis at later time. Sampler parts made of glass, polytetrafluoroethylene, and stainless steel so they do not react with sample.

Diaz, Vernon, Jr.↗

The air mycobiome is decoupled from the soil mycobiome in the California San Joaquin Valley

Abstract Dispersal is a key force in the assembly of fungal communities and the air is the dominant route of dispersal for most fungi. Understanding the dynamics of airborne fungi is important for determining their source and for helping to prevent fungal disease. This understanding is important in the San Joaquin Valley of California, which is home to 4.2 million people and where the airborne fungus Coccidioides is responsible for the most important fungal disease of otherwise healthy humans, coccidioidomycosis. The San Joaquin Valley is the most productive agricultural region in the United States, with the principal crops grown therein susceptible to fungal pathogens. Here, we characterize the fungal community in soil and air on undeveloped and agricultural land in the San Joaquin Valley using metabarcoding of the internal transcribed spacer 2 variable region of fungal rDNA. Using 1,002 individual samples, we report one of the most extensive studies of fungi sampled simultaneously from air and soil using modern sequencing techniques. We find that the air mycobiome in the San Joaquin Valley is distinct from the soil mycobiome, and that the assemblages of airborne fungi from sites as far apart as 160 km are far more similar to one another than to the fungal communities in nearby soils. Additionally, we present evidence that airborne fungi in the San Joaquin Valley are subject to dispersal limitation and cyclical intra‐annual patterns of community composition. Our findings are broadly applicable to understanding the dispersal of airborne fungi and the taxonomic structure of airborne fungal assemblages.

59 BASIC BIOLOGICAL SCIENCES↗

Quantitative Characterization of Impacts of Coupled Geomechanics and Flow on Safe and Permanent Geological Storage of CO 2 in Fractured Aquifers

This is the final scientific report for the award DE-FE0023305, entitled “Quantitative Characterization of Impacts of Coupled Geomechanics and Flow on Safe and Permanent Geological Storage of CO 2 in Fractured Aquifers.” The work has been divided into six tasks. In Task 2, we characterized rock properties, which are important when developing a quantitative approach for understanding and predicting geomechanical effects on large-scale CO 2 injection and long-term storage in the subsurface. Rock properties of interest for this characterization include porosity, permeability, elastic constants, strength, and heat capacity. We measured rock properties for three different rock types: concrete, sandstone and shale. These properties were obtained from the acoustic measurement, permeability and porosity measurement, Brazilian test, the uniaxial compressive test, and heat capacity measurement. Then, using the Brazilian technique to fracture samples, we measured their permeability under brine injection for varying effective stresses, followed by similar measurements of permeability under sc-CO 2 injection. Permeability to brine and sc-CO 2 decreased as the effective stress increased. The apparent permeability to sc-CO 2 was an order of magnitude less than that for brine, a consequence of CO 2 being the non-wetting fluid. In Task 3, we developed understandings and correlations for CO 2 injection pressure induced fracturing. We initially fractured four eight inch cubes of concrete with brine to establish a standard test procedure. Then, additional concrete samples were fractured using brine. Confining stresses were exerted on the samples and brine was injected at a constant rate into a borehole that was previously drilled into the concrete cube. The borehole pressure was measured and fracture initiation was identified as a peak in the pressure profile. That was followed by fracture propagation, which was identified as a plateau in the pressure profile, and finally the fracture reached the sample surface. The sample surfaces were photographed before and after fracturing, which enabled determination of where the fracture reached the sample surface. Afterwards, aqueous food dye solution was injected into the fractured concrete samples to color the fracture planes. The borehole was filled with food dye solution in advance, a gas pulse was transmitted to the borehole, and the borehole was then shut in to allow the food dye to be driven into existing fractures. Then, the concrete samples were broken down by high-pressure gas injection to reveal the geometry and morphology of the hydraulic fractures. In addition, acoustic measurements were conducted on multiple locations on each face of the concrete samples before and after injection for comparison. This comparison was used to confirm changes in the internal structure of the concrete sample, namely the formation of fractures. There were six concrete samples fractured with brine. Afterwards, concrete samples were fracture using sc-CO 2 . The main change in experimental procedure was the inclusion of temperature control, since in the field, we mostly encounter temperature and pressure conditions above the supercritical point of CO 2 . The concrete samples were pre-heated in an oven to elevate their temperature, and thermal tape was used to heat the CO 2 to a temperature above its supercritical temperature. Two concrete samples were fractured using liquid CO 2 , four concrete samples were fractured using gaseous CO 2 , and twenty two concrete samples were fractured using sc-CO 2 . For the concrete samples fractured using sc-CO 2 , three had pre-existing hydraulic fractures on the surface near the wellbore, and two were water saturated (as opposed to containing only air). Two concrete samples were composite samples, with a high permeability ball in the center, in order to represent CO 2 injection into a high permeability zone surrounded by a low permeability sealing formation. Later, we fractured five shale samples, obtained from the Niobrara shale outcrop, with sc-CO 2 . The injection rate was constant, confining stresses were applied, the shale samples were pre-heated in an oven to the desired temperature, and the sample was then fractured. An analysis of the failure type was done for many of the concrete samples, based on the predicted break down pressure for tensile and shear failure, and it was found that most samples fractured due to shear failure. Also, the presence of induced fractures has little to no effect on the fracture initiation pressure, but significantly changes the fracture morphology. The CO 2 fracturing in water saturated samples behaved much similar to brine induced fracturing. There was a significant difference of breakdown pressure for injection of CO 2 and brine, where the breakdown pressure for CO 2 induced fracturing is generally around the minimum horizontal stress and that for brine is much higher. Finally, the fracture orientation for most samples with large confining stress differential was perpendicular to the minimum horizontal stress. When the stress differential, especially the difference between the two directions with the smallest stresses was small, the fracture orientation was determined not only by the minimum stress direction, but also the magnitude of the confining stress, the tensile strength of the rock, and the breakdown pressure. In Task 4, we modified our coupled flow-geomechanical models to model fracture growth and propagation in storage formations and caprocks. These flow-geomechanical models are TOUGH2-CSM and TOUGH2-FLAC. The TOUGH2-CSM fluid and heat flow formulation is based on the TOUGH2 formulation of mass and energy conservation equations that govern fluid and heat flow in general multiphase, multicomponent, multi-porosity systems. The TOUGH2-CSM simplified geomechanical formulation is based on the linear theory of elasticity applied to multi-porosity non-isothermal (thermo-multi-poroelastic) media. We previously derived, from the fundamental relations of the linear theory of elasticity, an equation relating mean stress, pore pressures, temperatures, and body force (the Mean Stress equation) that we added to the TOUGH2-CSM fluid and heat flow equations. We extended the TOUGH2-CSM simplified geomechanical formulation to calculate the entire stress tensor by deriving equations for stress tensor components from derivatives of the Cartesian thermo-multi-poroelastic Navier equation components. In addition, we derived equations for stress tensor components in rz-coordinates. We solved these geomechanical equations using the integral finite difference method. This method utilizes momentum fluxes obtained by “factoring” a divergence operator out of each geomechanical equation. In Task 5, we did a literature survey to determine suitable correlations for fracture initiation, growth, and propagation. After surveying numerous papers, we modified TOUGH2-CSM to model stress dependent fracture initiation and growth using the Mohr-Coulomb criterion for shear failure in faults and caprock and the condition of negative minimum effective stress for tensile failure. Tensile failure results in a fracture whose width depends on the difference between fracture pressure and minimum stress and whose propagation is based on the difference between the stress intensity factor at the fracture tip and the rock toughness. The TOUGH-FLAC model is based on the FLAC3D ubiquitous joint model, extended for the modeling of permeability changes induced by changes in effective normal stress across fractures as well permeability changes caused by shearing along fractures. In Task 6, we validated our coupled flow-geomechanical models using analytical solutions and problems from the literature. We validated the TOUGH2-CSM modifications using analytical solutions to the displacement from a uniform load on a semi-infinite elastic medium and the two-dimensional Mandel-Cryer effect. Those were followed by a sample problem to test our stress tensor calculations, which was for injection into a single-phase reservoir with constant properties. Comparisons of our simulator to published results were done on for the depletion of a single-phase reservoir with stress dependent porosity, two examples from the In Salah gas project, an axisymmetric baserock–reservoir–caprock system with a normal faulting stress regime that had thermally induced shear stresses, simulations of CO 2 leakage through caprock in a two-dimensional reservoir in Cartesian coordinates, and predictions of caprock failure from CO 2 injection into an axisymmetric reservoir. Finally, we simulated CO 2 injection pressure-induced fracturing from one of our laboratory studies, Sample 39, and obtained a fracture profile. We also validated the TOUGH2-FLAC model for fluid driven fracture growth against solutions based on the KGD model and a case with an inclined fracture that was loaded from the boundaries to achieve wing-crack propagation. The strain softening tensile behavior and softening of modulus considering a simple damage approach was verified by a simulation representing hydraulic fracturing stress measurement around a vertical well. Finally, the model was validated against deep fracture zone opening and surface uplift at In Salah with inverses analysis used to improve the match of simulation with field data. In Task 7, we developed a scheme based on inverse modeling that can be used to identify caprock leakage. Injection of fluid into a reservoir results in a time varying pressure profile that depends on the properties of the rock and the fluid. The presence of significant caprock leakage would effect this pressure profile and we used inverse modeling, namely the Levenberg-Marquardt method, to determine the leakage location from the pressure profile. A two-dimensional and a three-dimensional example based on published data were presented. The published simulation was run and its results were considered as “field” data. In the two-dimensional example, a simulation of CO 2 injection into a two-dimensional aquifer-caprock system, the caprock had a vertical fault through which leakage could occur. The location of this leakage was obtained from our inverse modeling scheme. In the three-dimensional example, the simulation domain had four geological layers, one of which was the injection zone that contained a horizontal injection well. We simulated fractures as high permeability gridblocks, introduced a fracture that spanned the caprock depth, and ran a simulation to obtain “field” data. Then, using our inverse modeling scheme, we obtained the location of that fracture.

58 GEOSCIENCES↗

A summary of air sampler filter performance data: Bladewerx Speclon 5(TM) and Millipore FMLW047 5um

Bladewerx™ LLC (Rio Rancho, NM) manufactures instrumentation, neutron shielding and activation foils for the radiation protection industry. Specializing in portable alpha/beta air monitors and sample counters, Bladewerx is the source of Speclon 5™ PTFE filter media that they recommend for high-resolution alpha spectroscopy. Los Alamos National Laboratory (LANL) utilizes Speclon™ filter material in CAM (Continuous Air Monitor) samplers for workplace air monitoring. Millipore FMLW (5μm) filters are also used at Los Alamos, and a comparison of the two filter types has been requested. For filter face air velocities from 0.066 m/s to 1.5 m/s, the aerosol collection efficiency (for 0.3 μm particle diameters) and the filter pressure drops were measured. The FWHM (full width half maximum) of alpha spectroscopy peaks was also determined, using naturally occurring radon progeny at an alpha energy of 6 MeV.

61 RADIATION PROTECTION AND DOSIMETRY↗

COMBLE Ice Nucleating Particle Measurements

These data list ice nucleating particle (INP) number concentrations active in the immersion freezing mode per large volumes of air collected using filters, sampled atop the AOS trailer, part of AMF1, sited at Nordmela Harbor, Andøya Island, Norway, from 01 December 2019 to 26 May 2020, as part of the Cold-air Outbreaks in the Marine Boundary Layer Experiment (COMBLE). Collections were made over periods of 6 to 74 hours (average 34 h and 42 m3 filtered), with periods tailored to integrate cold-air outbreaks or flanking periods of non-cold-air outbreak air. We used open-faced polycarbonate filters that were sampled at a height of 4 m AGL on the AOS trailer (6 m below its inlet), 6-8 m ASL and 30 m inland from the harbor wall, and near the other AMF measurements. Filters were stored and returned frozen to Colorado State University (CSU), where immersion freezing measurements over a range from 0 to typically -28°C were made using the CSU Ice Spectrometer (IS). This first entailed the removal of particles (agitation of filter in 0.1 µm filtered ultrapure water) from filters to create aliquot suspensions that were subdivided (and frozen) for subsequent analyses. One portion was used to obtain a basic temperature spectrum of INP number concentrations on the basis of the freezing of an array of smaller liquid aliquots during cooling, and relation of the frozen fraction to the total air volume sampled. A subset of other portions of the original suspension aliquots were heat treated (95°C for 20 min) to denature biological INPs (a reduction in concentrations reveals the proportion of all INPs that were likely of biological origin, such as microbial or proteinaceous) and digested in 10% H2O2 at 95°C under UV-B illumination to remove all organic carbon INPs; the residual is presumed to be inorganic (likely mineral) INPs. Other samples have been archived frozen for future potential testing of INP source compositions and aerosol chemical and biological source attribution.

54 ENVIRONMENTAL SCIENCES↗

Analysis of 85Kr: a comparison at the 10-14 level using micro-liter samples

The isotopic abundance of 85Kr in the atmosphere, currently at the level of 10211, has increased by orders of magnitude since the dawn of nuclear age. With a half-life of 10.76 years, 85Kr is of great interest as tracers for environmental samples such as air, groundwater and ice. Atom Trap Trace Analysis (ATTA) is an emerging method for the analysis of rare krypton isotopes at isotopic abundance levels as low as 10214 using krypton gas samples of a few micro-liters. Both the reliability and reproducibility of the method are examined in the present study by an inter-comparison among different instruments. The 85Kr/Kr ratios of 12 samples, in the range of 10213 to 10210, are measured independently in three laboratories: a low-level counting laboratory in Bern, Switzerland, and two ATTA laboratories, one in Hefei, China, and the other in Argonne, USA. The results are in agreement at the precision level of 5%.

MASS SPECTROMETRY↗

Measuring aerosol collection efficiency for the Bladewerx “New Speclon TM 5” and the older “Speclon TM 5” filter

Bladewerx TM LLC (Rio Rancho, NM) manufactures instrumentation, neutron shielding and activation foils for the radiation protection industry. Specializing in portable alpha/beta air monitors and sample counters, Bladewerx is the source of Speclon TM PTFE filter media that they recommend for high-resolution alpha spectroscopy. Los Alamos National Laboratory (LANL) utilizes Speclon TM filter material in CAM (Continuous Air Monitor) samplers for workplace air monitoring. The LANL Aerosol Engineering Facility received air filter material from Bladewerx, referred to as “New Speclon 5” in this document, in order to distinguish from filter material that was previously received (referred to as “Speclon 5” in this document). In this document, the aerosol collection efficiency and airflow resistance (pressure drop) were measured for the New Speclon 5 filter material.

61 RADIATION PROTECTION AND DOSIMETRY↗

Two-color interferometry and shadowgraphy characterization of an orthogonal double-pulse laser ablation

Orthogonal double pulse laser ablation on aluminum target at atmospheric pressure was studied by time-resolved optical emission spectroscopy, shadowgraphy and two-color interferometry. Studies were realized as a function of the distance from the first pulse plasma induced in air to the sample surface. The evolution of the electron and neutral particles densities were determined by two-color interferometry. Line intensification mechanisms are discussed based on the interferometry results and the plumes interaction dynamics. It was found that the sample heating by the preablation pulse could contribute to the observed emission enhancement.

36 MATERIALS SCIENCE↗

Conductivity, structure, and thermodynamics of Y 2 Ti 2 O 7 –Y 3 NbO 7 solid solutions

The defect fluorite yttrium niobate Y 3 NbO 7 and pyrochlore yttrium titanate Y 2 Ti 2 O 7 solid solutions have been synthesized via a solid state synthesis route. The resulting stoichiometry of the oxides is Y 2+x Ti 2-2x Nb x O 7 , where x = 0 to x = 1. All of the samples were single-phase; however, for those with a predominant fluorite phase, a small amount of additional pyrochlore phase was detected. The volume of the solid solution unit cells linearly increases with increase in yttrium niobate content. The water uptake increases with (x) and the protonic defect concentration reaches almost 4.5 × 10 -3 mol mol -1 at 300 °C. The calculated enthalpy of formation from oxides suggests strong stability for all of the compositions, with the values of enthalpy ranging from -84.6 to -114.3 kJ mol -1 . The total conductivity does not have a visible dependence on Y 3 NbO 7 content. For each compound, the total conductivity is higher in wet air. Interestingly, for samples where x < 0.5, the ratio of conductivity in hydrogen to air increases with increasing temperature, while for x > 0.5, the trend is the opposite.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during August-September 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur- and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds. Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C 10-12 ) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.

54 ENVIRONMENTAL SCIENCES↗

Impacts of a Prescribed Fire on Air Quality in Central New Mexico

A short-duration but high-impact air quality event occurred on 28 November 2018 along the Rio Grande Valley of New Mexico. This fire occurred outside the typical wildfire season, and greatly impacted the air quality in Socorro, NM, and the surroundings. Measurements were taken during the event using an aerosol light scattering technique (integrating nephelometer) and a particulate mass concentration monitor (DustTrak PM optical monitor). The instruments sampled the ambient air during the event on the campus of the New Mexico Institute of Mining and Technology in Socorro, New Mexico. The peak values on a 5-min basis of light scattering and the PM mass concentration reached 470 Mm -1 and 270 µg/m 3 , respectively. We examined the meteorological context of the event using local meteorological data and back trajectories using the NOAA HYSPLIT model to determine atmospheric transport and possible sources. Several fires, both prescribed and wildfires, occurred in the region including a prescribed burn at Bosque del Apache National Wildlife Refuge (17 km south-southeast of the receptor site). The data suggest that the prescribed burn at Bosque del Apache was the dominant contributor due to transport evidence and the event’s narrow spatiotemporal extent. The increasing importance of restoring ecosystem function using prescribed fire in wildland fire management will likely lead to more frequent air quality impacts and sets up policy tradeoffs that require a balance between these public goals. This study examines the evidence of the effects of a prescribed fire in a protected wildland area impacting the air quality in a nearby populated area.

54 ENVIRONMENTAL SCIENCES↗

Effect Of Oxidation On Chromium Leaching And Redox Capacity Of Slag-Containing Waste Forms

The rate of oxidation is important to the long-term performance of reducing salt waste forms because the solubility of some contaminants, e.g., technetium, is a function of oxidation state. TcO 4 - in the salt solution is reduced to Tc(IV) and has been shown to react with ingredients in the waste form to precipitate low solubility sulfide and/or oxide phases [Shuh, et al., 1994, Shuh, et al., 2000, Shuh, et al., 2003]. Upon exposure to oxygen, the compounds containing Tc(IV) oxidize to the pertechnetate ion, Tc(VII)O 4 - , which is very soluble. Consequently the rate of technetium oxidation front advancement into a monolith and the technetium leaching profile as a function of depth from an exposed surface are important to waste form performance and ground water concentration predictions. An approach for measuring contaminant oxidation rate (effective contaminant specific oxidation rate) based on leaching of select contaminants of concern is described in this report. In addition, the relationship between reduction capacity and contaminant oxidation is addressed. Chromate was used as a non-radioactive surrogate for pertechnetate in simulated waste form samples. Depth discrete subsamples were cut from material exposed to Savannah River Site (SRS) field cured conditions. The subsamples were prepared and analyzed for both reduction capacity and chromium leachability. Results from field-cured samples indicate that the depth at which leachable chromium was detected advanced further into the sample exposed for 302 days compared to the sample exposed to air for 118 days (at least 50 mm compared to at least 20 mm). Data for only two exposure time intervals is currently available. Data for additional exposure times are required to develop an equation for the oxidation front progression. Reduction capacity measurements (per the Angus-Glasser method, which is a measurement of the ability of a material to chemically reduce Ce(IV) to Ce(III) in solution) performed on depth discrete samples could not be correlated with the amount of chromium leached from the depth discrete subsamples or with the oxidation front inferred from soluble chromium (i.e., effective Cr oxidation front). Exposure to oxygen (air or oxygen dissolved in water) results in the release of chromium through oxidation of Cr(III) to highly soluble chromate, Cr(VI). Residual reduction capacity in the oxidized region of the test samples indicates that the remaining reduction capacity is not effective in re-reducing Cr(VI) in the presence of oxygen. Consequently, this method for determining reduction capacity may not be a good indicator of the effective contaminant oxidation rate in a relatively porous solid (40 to 60 volume percent porosity). The chromium extracted in depth discrete samples ranged from a maximum of about 5.8 % at about 5 mm (118 day exposure) to about 4 % at about 10 mm (302 day exposure). The use of reduction capacity as an indicator of long-term performance requires further investigation. The carbonation front was also estimated to have advanced to at least 28 mm in 302 days based on visual observation of gas evolution during acid addition during the reduction capacity measurements. Depth discrete sampling of materials exposed to realistic conditions in combination with short term leaching of crushed samples has potential for advancing the understanding of factors influencing performance and will support conceptual model development.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗