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At least 109 records · Page 6

A new method for the preparation of polymeric porous layer open tubular columns for GC application

A new method to prepare polymeric PLOT columns by using in situ polymerization technology is described. The method involves a straightforward in situ polymerization of the monomer. The polymer produced is directly coated on the metal tubing. This eliminates many of the steps needed in conventional polymeric PLOT column preparation. Our method is easy to operate and produces very reproducible columns, as shown previously (T. C. Shen. J. Chromatogr. Sci. 30, 239, 1992). The effects of solvents, tubing pretreatments, initiators and reaction temperatures in the preparation of PLOT columns are studied. Several columns have been developed to separate (1) highly polar compounds, such as water and ammonia or water and HCN, and (2) hydrocarbons and inert gases. A recent improvement has allowed us to produce bonded polymeric PLOT columns. These were studied, and the results are included also.

NASA Discipline Exobiology↗

Gas chromatographic column for the storage of sample profiles

The concept of a sample retention column that preserves the true time profile of an analyte of interest is studied. This storage system allows for the detection to be done at convenient times, as opposed to the nearly continuous monitoring that is required by other systems to preserve a sample time profile. The sample storage column is essentially a gas chromatography column, although its use is not the separation of sample components. The functions of the storage column are the selective isolation of the component of interest from the rest of the components present in the sample and the storage of this component as a function of time. Using octane as a test substance, the sample storage system was optimized with respect to such parameters as storage and readout temperature, flow rate through the storage column, column efficiency and storage time. A 3-h sample profile was collected and stored at 30 degrees C for 20 h. The profile was then retrieved, essentially intact, in 5 min at 130 degrees C.

NASA Program Exobiology↗

Calculation of Centrally Loaded Thin-Walled Columns Above the Buckling Limit

When thin-walled columns formed from flanged sheet, such as used in airplane construction, are subjected to axial load, their behavior at failure varies according to the slenderness ratio. On long columns the axis deflects laterally while the cross section form is maintained; buckling results. The respective breaking load in the elastic range is computed by Euler's formula and for the plastic range by the Engesser- Karman formula. Its magnitude is essentially dependent upon the length. On intermediate length columns, especially where open sections are concerned, the cross section is distorted while the cross section form is preserved; twisting failure results. The buckling load in twisting is calculated according to Wagner and Kappus. On short columns the straight walls of low-bending resistance that form the column are deflected at the same time that the cross section form changes - buckling occurs without immediate failure. Then the buckling load of the total section computable from the buckling loads of the section walls is not the ultimate load; quite often, especially on thin-walled sections, it lies considerably higher and is secured by tests. Both loads, the buckling and the ultimate load are only in a small measure dependent upon length. The present report is an attempt to theoretically investigate the behavior of such short, thin-walled columns above the buckling load with the conventional calculating methods.

Reinitzhuber, F.↗

Measurements of Nitrogen Dioxide Total Column Amounts using a Brewer Double Spectrophotometer in Direct Sun Mode

NO2 column amounts were measured for the past 2 years at Goddard Space Flight Center, Greenbelt, Maryland, using a Brewer spectrometer in direct Sun mode. A new bootstrap method to calibrate the instrument is introduced and described. This technique selects the cleanest days from the database to obtain the solar reference spectrum. The main advantage for direct Sun measurements is that the conversion uncertainty from slant column to vertical column is negligible compared to the standard scattered light observations where it is typically on the order of 100% (2sigma) at polluted sites. The total 2sigma errors of the direct Sun retrieved column amounts decrease with solar zenith angle and are estimated at 0.2 to 0.6 Dobson units (DU, 1 DU approx. equal to 2.7 10(exp 16) molecules cm(exp -2)), which is more accurate than scattered light measurements for high NO2 amounts. Measured NO2 column amounts, ranging from 0 to 3 DU with a mean of 0.7 DU, show a pronounced daily course and a strong variability from day to day. The NO2 concentration typically increases from sunrise to noon. In the afternoon it decreases in summer and stays constant in winter. As expected from the anthropogenic nature of its source, NO2 amounts on weekends are significantly reduced. The measurements were compared to satellite retrievals from Scanning Image Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY). Satellite data give the same average NO2 column and show a seasonal cycle that is similar to the ground data in the afternoon. We show that NO2 must be considered when retrieving aerosol absorption properties, especially for situations with low aerosol optical depth.

Cede, Alexander↗

Intercomparison of SCIAMACHY and OMI Tropospheric NO2 Columns: Observing the Diurnal Evolution of Chemistry and Emissions from Space

Concurrent (August 2006) measurements of tropospheric NO2 columns from OMI aboard Aura (1330 local overpass time) and SCIAMACHY aboard Envisat (1000 local overpass time) offer an opportunity to examine the consistency between the two instruments under tropospheric background conditions and the effect of different observing times. For scenes with tropospheric NO 2 columns <5.0 x 10(exp 15) molecules cm 2, SCIAMACHY and OMI agree within 1.0-2.0 x 10(exp 15) molecules cm 2, consistent with the detection limits of both instruments. We find evidence for a low bias of 0.2 x 10(exp 15) molecules cm 2 in OMI observations over remote oceans. Over the fossil fuel source regions at northern midlatitudes, we find that SCIAMACHY observes up to 40% higher NO2 at 1000 local time (LT) than OMI at 1330 LT. Over biomass burning regions in the tropics, SCIAMACHY observes up to 40% lower NO 2 columns than OMI. These differences are present in the spectral fitting of the data (slant column) and are augmented in the fossil fuel regions and dampened in the tropical biomass burning regions by the expected increase in air mass factor as the mixing depth rises from 1000 to 1330 LT. Using a global 3-D chemical transport model (GEOS-Chem), we show that the 1000-1330 LT decrease in tropospheric NO2 column over fossil fuel source regions can be explained by photochemical loss, dampened by the diurnal cycle of anthropogenic emissions that has a broad daytime maximum. The observed 1000-1330 LT NO2 column increase over tropical biomass burning regions points to a sharp midday peak in emissions and is consistent with a diurnal cycle of emissions derived from geostationary satellite fire counts.

Boersma, K. Folkert↗

Comparison of Surface and Column Variations of CO2 Over Urban Areas for Future Active Remote CO2 Sensors

High resolution in-situ CO2 measurements were recorded onboard the NASA P-3B during the DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) Field Campaign, to investigate the ability of space-based observations to accurately assess near surface conditions related to air quality. This campaign includes, Washington DC/Baltimore, MD (July 2011), San Joaquin Valley, CA (January - February 2013), Houston, TX (September 2013), and Denver, CO (July-August 2014). Each of these campaigns consisted of missed approaches and approximately two hundred vertical soundings of CO2 within the lower troposphere (surface to about 5 km). In this study, surface (0 - 1 km) and column-averaged (0 - 3.5 km) CO2 mixing ratio values from the vertical soundings in the four geographically different urban areas are used to investigate the temporal and spatial variability of CO2 within the different urban atmospheric emission environments. Tracers such as CO, CH2O, NOx, and NMHCs are used to identify the source of CO2 variations in the urban sites. Additionally, we apply nominal CO2 column weighting functions for potential future active remote CO2 sensors operating in the 1.57-microns and 2.05-microns measurement regions to convert the in situ CO2 vertical mixing ratio profiles to variations in CO2 column optical depths, which is what the active remote sensors actually measure. Using statistics calculated from the optical depths at each urban site measured during the DISCOVER-AQ field campaign and for each nominal weighting function, we investigate the natural variability of CO2 columns in the lower troposphere; relate the CO2 column variability to the urban surface emissions; and show the measurement requirements for the future ASCENDS (Active Sensing of CO2 Emissions over Nights, Days, and Seasons) in the continental U.S. urban areas.

Choi, Yonghoon↗

The Two-Column Aerosol Project: Phase I - Overview and Impact of Elevated Aerosol Layers on Aerosol Optical Depth

The Two-Column Aerosol Project (TCAP), conducted from June 2012 through June 2013, was a unique study designed to provide a comprehensive data set that can be used to investigate a number of important climate science questions, including those related to aerosol mixing state and aerosol radiative forcing. The study was designed to sample the atmosphere be tween and within two atmospheric columns; one fixed near the coast of North America (over Cape Cod, MA) and a second moveable column over the Atlantic Ocean several hundred kilometers from the coast. The U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF) was deployed at the base of the Cape Cod column, and the ARM Aerial Facility was utilized for the summer and winter intensive observation periods. One important finding from TCAP is that four of six nearly cloud-free flight days had aerosol layers aloft in both the Cape Cod and maritime columns that were detected using the nadir pointing second-generation NASA high-spectral resolution lidar (HSRL-2).These layer s contributed up to 60 of the total observed aerosol optical depth (AOD). Many of these layers were also intercepted by the aircraft configured for in situ sampling, and the aerosol in the layers was found to have increased amounts of biomass burning material and nitrate compared to aerosol found near the surface. In addition, while there was a great deal of spatial and day-to-day variability in the aerosol chemical composition and optical properties, no systematic differences between the two columns were observed.

aerosols↗

Is There an Optimal CO2 Partial Column for Flux Inversions?

The fidelity of flux estimates from an atmospheric inversion depends on the ability of atmospheric transport models to simulate the measured quantity. For species such as CO2, with surface fluxes and a large network of surface measurements, this means correctly simulating the dynamics of the planetary boundary layer (PBL), which is one of the most uncertain aspects of atmospheric transport modeling. In contrast, the simulated total column average mole fraction of CO2 (XCO2) is largely insensitive to simulated PBL dynamics. Therefore, measurements of XCO2 provided by current and future short wave infrared (SWIR) greenhouse gas (GHG) satellites such as GOSAT and the OCO family would seem to be more appropriate to flux inversions, as far as minimizing transport model errors (the "noise") is concerned. Unfortunately, the flux-induced variation of CO2 (the "signal") is the largest within the PBL and smallest in XCO2. Therefore, assimilating XCO2 as opposed to PBL CO2 need not give us the strongest "signal to noise" in flux inversions. Recent work on GOSAT and OCO2 retrievals suggest that SWIR satellite spectra may be used to estimate a lower partial column CO2, which could be assimilated in a flux inversion, instead of XCO2.Here we report on a study to assess whether there is an optimal partial column average CO2, intermediate between PBL CO2 and XCO2, whose assimilation might yield the best signal to noise in flux inversions, where (as before) "signal" is the flux-induced variation and "noise" is the error in transport modeling. We simulate atmospheric CO2 with five different global transport models and a common surface CO2 flux over ten years. We consider the spread across the five models to be a proxy for transport model error (the "noise"), and the common variation of CO2 in all five models to be a proxy for the "signal". We compare these signals and noises at different spatiotemporal scales for different partial column specifications to investigate whether there exists an optimal partial column that has large surface flux-driven variations and yet is relatively insensitive to errors in transport models. Finally, we comment on the feasibility of estimating such a partial column from current and future SWIR GHG satellites in the light of recent work on vertically resolved CO2 from current SWIR GHG satellites.

Basu, Sourish↗

Generation of High Frequency Response in a Dynamically Loaded, Nonlinear Soil Column

Detailed guidance on linear seismic analysis of soil columns is provided in “Seismic Analysis of Safety-Related Nuclear Structures and Commentary (ASCE 4, 1998),” which is currently under revision. A new Appendix in ASCE 4-2014 (draft) is being added to provide guidance for nonlinear time domain analysis which includes evaluation of soil columns. When performing linear analysis, a given soil column is typically evaluated with a linear, viscous damped constitutive model. When submitted to a sine wave motion, this constitutive model produces a smooth hysteresis loop. For nonlinear analysis, the soil column can be modelled with an appropriate nonlinear hysteretic soil model. For the model in this paper, the stiffness and energy absorption result from a defined post yielding shear stress versus shear strain curve. This curve is input with tabular data points. When submitted to a sine wave motion, this constitutive model produces a hysteresis loop that looks similar in shape to the input tabular data points on the sides with discontinuous, pointed ends. This paper compares linear and nonlinear soil column results. The results show that the nonlinear analysis produces additional high frequency response. The paper provides additional study to establish what portion of the high frequency response is due to numerical noise associated with the tabular input curve and what portion is accurately caused by the pointed ends of the hysteresis loop. Finally, the paper shows how the results are changed when a significant structural mass is added to the top of the soil column.

nonlinear↗

Testing Results from the Low Activity Waste Pretreatment System (LAWPS) Full-Scale Ion Exchange Column Test and Engineering Scale Integrated System Test - 18634

The U.S. Department of Energy (DOE), Office of River Protection's (ORP) primary mission is to retrieve and treat Hanford's tank waste and close the Tank Farms to protect the Columbia River. Mixed radioactive waste is stored in 177 underground tanks at the Hanford Site as reported in DOE/ORP 2003- 02, Environmental Impact Statement for Retrieval, Treatment, and Disposal of Tank Waste and Closure of the Single Shell Tanks at the Hanford Site, Richland WA, Inventory and Source Term Data Package. The 177 underground tanks are estimated to contain about 56 million gallons of waste. The Low Activity Waste Pretreatment System (LAWPS) Project provides for the early production of immobilized low activity waste (ILAW) by feeding LAW directly from Tank Farms to the Hanford Waste Treatment Plant's (WTP's) LAW Facility, bypassing the Pretreatment Facility. Prior to the transfer of feed to the WTP LAW Vitrification Facility, tank supernatant waste will be pretreated in the LAWPS to meet the WTP LAW waste acceptance criteria. The LAWPS will also facilitate the return of secondary liquid wastes from the WTP LAW Vitrification Facility to the Tank Farms. In November of 2015 DOE's Tank Operations Contractor, Washington River Protection Solutions (WRPS), awarded a contract to the AECOM team to design, fabricate and operate two test platforms to generate performance data at two different scales and demonstrate technology maturation. The first platform models the ion exchange (IX) columns at full scale, and the second platform models the integrated flowsheet (cross flow filter (CFF) and IX) at 1/9. scale. Overarching technical objectives of performing the full-scale ion exchange test and the engineering-scale integrated test are to: 1. Test interactions between unit process operations; 2. Test removal of non-radioactive cesium from process stream; 3. Test removal of undissolved solids from process stream; 4. Confirm operational flow rate range and stability; 5. Confirm volumetric throughput of waste stream over flow operating range; 6. Confirm range of process temperatures over planned operating range; 7. Establish system hydraulics and process criteria; 8. Coordinate key control and monitoring components; 9. Establish treated product chemistry meets requirements (cesium, solids, and pH); and 10. Test the hazard control strategy for a no flow condition through the IX column. Data collected during testing will be used by WRPS to validate the preliminary design, inform the final design of the permanent plant equipment, and demonstrate that the critical technology elements have advanced to a technology readiness level of 6 (prototypical system validation in a relevant environment). Testing on both platforms started in fall of 2016 generating NQA-1 data. This paper covers test results from the first five phases of testing on the 1/9. scale integrated test platform. A further three phases of testing are currently being executed, these including a 5.6 M sodium simulant containing foulant, a high viscosity simulant and finally a run performed with a lower Cs concentration (all earlier tests were spiked to 4 x Cs to reduce volume and cost). Results from these tests were not available at the time of writing available. Results are also presented from the full scale IX testing. Eight test were performed covering column loading, elution and regeneration; column loading, elution and regeneration with upflow displacement; IX column loading and gas migration; resin removal; solids accumulation; and IX column emergency recirculation and vent. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Plasma Bubble Column Reactor: A High Throughput Reactor Design for Water Treatment

Plasma-based water treatment (PWT) is a promising technology that can degrade various emerging contaminants. However, PWT application on an industrially viable scale is hindered by the lack of an efficient reactor design that combines enhanced plasma-liquid contact with high liquid throughput. This work investigates the applicability of a bubble column gas-liquid contactor to PWT. A pulsed plasma bubble column reactor (PBCR) with a concentric rod-cylinder electrode configuration was used to correlate contaminant removal performance with the gas-liquid contact parameters of the bubble column. A surfactant, rhodamine B dye, and a nonsurfactant, caffeine, were used as model contaminants at µM concentration levels. The bubble column characteristics, i.e., gas holdup, bubble size distribution, and gas-liquid area, were measured as a function of superficial gas velocity using image-based methods. Degradation rates of both contaminants increased with gas flowrate. For caffeine, the increase was attributed to intensified bulk liquid mixing, while dye degradation increased due to the increased gas-liquid area. Ultimately, we show that bubble column contactors significantly improve the utilization of plasma-generated reactive species toward contaminant degradation by distributing them over a large contact area. As a result, a better match between the plasma species interfacial flux and the interfacial contaminant concentration leads to improved treatment energy efficiency. Furthermore, typical degradation energy efficiencies were ~10 g/kWh for caffeine and ~60 g/kWh for rhodamine B.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrodynamics of countercurrent flow in an additive-manufactured column with triply periodic minimal surfaces for carbon dioxide capture

Computational investigation of the countercurrent flows in an additively manufactured (AM) column packed with triply periodic minimal surface (TPMS) is challenging. Multiphase flow simulations using the volume of fluid (VOF) method can explain the column’s hydrodynamic characteristics, including interfacial area, liquid holdup, pressure drop, flow regime, etc. The interfacial area is a key factor dictating the mass transfer via the absorption process, and thereby the overall efficiency of the column. The impacts of a solvent's physical properties, liquid and gas loads, and contact angle on the hydrodynamics are extensively explored. The solvents include traditional solvent (monoethanolamine [MEA]) used in industry as well as a water-lean solvent (EEMPA) as prospective solvents for carbon capture. As expected, interfacial area and liquid holdup increase with increasing liquid loads (q L ). The EEMPA exhibits higher values for the interfacial area and liquid holdup compared to those for the MEA. The dry and wet pressure drops per unit length in the column at different gas loads (F G ) are calculated and further compared with the empirical correlations for traditional packings. At low gas loads, i.e., in the preloading regime, the predicted values of the wet and dry pressure drops match well with the corresponding values calculated from available correlations. The gas load has a marginal impact on the interfacial area at its lower value, but the higher value of F G (>2.18 $\sqrt{Pa}$) causes flooding in the column. The effect of varying contact angles on the interfacial area and liquid holdup in the preloading regime is also studied. Both interfacial area and liquid holdup decrease with the increase in the value of the contact angle. Altogether, the effect of the contact angle on interfacial area is more pronounced than other parameters influencing the interfacial area.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Void fraction, bubble size and interfacial area measurements in co-current downflow bubble column reactor with microbubble dispersion

Micro-bubbles dispersed in bubble column reactors have received great interest in recent years, due to their small size, stability, high gas-liquid interfacial area concentrations and longer residence times. The high gas-liquid interfacial area concentrations lead to high mass transfer rates compared to conventional bubble column reactors. In the present work, experiments have been performed in a down-flow bubble column reactor with micro-bubbles generated and dispersed by a novel mechanism to determine the gas-liquid interfacial area concentrations by measuring the void fraction and bubble size distributions. Gamma-ray densitometry has been employed to determine the axial and radial distributions of void fraction and a high speed camera equipped with a borescope is used to measure the axial and radial variations of bubble sizes. Also, the effects of superficial gas and liquid velocities on the two-phase flow characteristics have been investigated. Further, reconstruction techniques of the radial void fraction profiles from the gamma densitometry's chordal measurements are discussed and compared for a bubble column reactor with dispersed micro-bubbles. The results demonstrate that the new bubble generation technique offers high interfacial area concentrations (1,000 to 4,500 m 2 /m 3 ) with sub-millimeter bubbles (500 to 900 µm) and high overall void fractions (10% – 60%) in comparison with previous bubble column reactor designs. The void fraction data was analyzed using slip velocity model and empirical correlation has been proposed to predict the Sauter mean bubble diameter.

09 BIOMASS FUELS↗

Influence of porous aluminosilicate grain size materials in experimental and modelling Cs + adsorption kinetics and wastewater column process

This paper focuses on the influence of the grain size of a geopolymer based adsorbent on its Cs + adsorption performances both in batch and fixed-bed process. The geopolymer phase was used as a binder to support NaY zeolite particle in a 20 wt% charged porous composite with 160 m 2 .g –1 of porous surface area. These samples were shaped with three grain sizes (50 /100/500 µm) to remove 80–90 mg/g of Cs + in batch and column operations. After their microstructural and porous characterizations, their efficiency and adsorption characteristics were investigated through adsorption isotherms and kinetic in the two processes. While the grain size has no influence on the maximal extraction capacity of the adsorbent, it strongly affects the sorption kinetic. By coupling experimental data and a modelling approach, the complex sorption mechanism was highlighted, suggesting a new insight of the contaminant sorption kinetic. Then, comparison of batch and column adsorption experiments illustrates the detailed explanation of various process parameters for column study. The results show challenges for fixed-bed column utilization by the choice of the appropriate grain size as a compromise between the material sorption kinetic and hydrodynamic considerations. Furthermore, this is of high importance to more accurately optimize the design of column adsorption to assess the transport of Cs+ in multi-porous tailored grain size materials.

36 MATERIALS SCIENCE↗

Multiphase Large Eddy Simulation of a Pulsed Sieve-Plate Extraction Column - 18125

Presented here is research resulting from a framework of single-phase and multiphase modelling trials. These are intended to accurately simulate the internal flow phenomena arising in pulsed sieve-plate extraction columns representative of those found in industry. Three-dimensional unsteady flow calculations using large eddy simulation coupled with dynamic sub-grid scale modelling have been used to capture the transient effects of sinusoidal flow conditions using the open source CFD code OpenFOAM{sup R}. Multiphase interface interactions are modelled using the volume of fluid method with appropriate heavy and light phase fluidic properties capturing surface tension, density and viscous effects. The system studied consists of a 150 mm diameter column with two perforated plates with a fractional free area of 25 %, operational under 1 Hz pulsing frequency at a 50 mm amplitude and plate spacing of 300 mm. The materials simulated include water (single-phase) and 3 M nitric acid and dodecane / tributyl phosphate mixture at 30 vol% (multiphase). Results are compared with appropriate correlations from literature. The dispersive mixing efficiency of the system was also evaluated via a mixing index value which allows quantification of the ratio of rotational and irrotational flow components. This study has found that the predictive methods employed are effective at capturing the different scales of turbulence present within pulsed sieve-plate extraction columns, and its influence on their operation. As such, the work highlights the ability of large eddy simulation-based modelling to predict the complex flows in such column geometries. Furthermore, the techniques employed provide valuable insight into the hydrodynamic flow characteristics and mixing mechanisms arising within pulsed sieve-plate extraction columns. (authors)

42 ENGINEERING↗

Ion Exchange Column Thermal Modeling: Prevention of Process Effluent Boiling - 18577

The Savannah River Site treats and disposes of legacy high-level waste, which resulted from 60 years of nuclear material production, medical research, and other nuclear related work. Complex mixtures of soluble and insoluble solids occupy tanks of which the South Carolina Department of Health and Environmental Control recognizes as the single largest environmental risk state-wide. The risk is reduced through removal, treatment, and solidification of decontaminated salt waste. Presently, SRS decontaminates the soluble salt component of the waste, a solution containing actinides and cesium, via implementation of the Actinide Removal Process and the Modular Caustic Side Solvent- Extraction Unit. Caustic solvent extraction is set to increase in scale by late 2018, with startup of the newly constructed Salt Waste Processing Facility. In conjunction with Salt Waste Processing Facility startup, Savannah River Remediation has been tasked by the Department of Energy to demonstrate modular ion exchange technology. The Tank Closure Cesium Removal project aims to demonstrate the feasibility of modular ion exchange processes for future Department of Energy applications. The Tank Closure Cesium Removal system is scheduled to begin operation in mid-2018. Dissolved salt solution, or influent, will be fed through a filter and ion exchange columns in lead-lag configuration, producing effluent. The effluent is fed to a separate high-level waste tank, for future disposition at Salt-stone Production Facility. Once the demonstration project is complete, the loaded ion exchange columns will be purged, dried, and placed in interim safe storage, awaiting final disposition. The ion exchange media selected for the Tank Closure Cesium Removal system is Honeywell UOP IONSIV{sup C} R-9120. The media is a prime candidate for separation of cesium from radioactive high-level waste. UOP R-9120{sup C} is inorganic and has high capacity, selectivity, and affinity for cesium. During operation, influent is fed to the ion exchange columns, contacting UOP R-9210{sup C} packed within the media vessel. Contact initiates loading of isotopes, and given ample time the solid phase (ion exchange media) and solution achieve thermodynamic equilibrium. UOP R-9120{sup C} is a prime candidate for separation of cesium and dissolved fission products. Although the properties of UOP R-9120{sup C} are favorable for separation, the same properties lead to accumulation of a heat source in the ion exchange bed. Cesium-137 and its daughter product, barium-137 m, generate a clear majority of heat (i.e. ∼ 94%). During operation salt solution flows through each column and transports heat from the ion exchange bed. Once operation is terminated, the effluent contained within the porous bed volume becomes essentially static. In the absence of engineering controls, the heat generated may boil the effluent. Rapid vaporization of aqueous salt solution would lead to bed over pressurization. Over pressurization and an associated release of high-level waste would result in adverse impacts to human health and the environment. This paper focuses on modeling the heat transfer associated with the Tank Closure Cesium Removal system ion exchange column. The model evaluates the maximum heat generation and the associated radionuclide loadings that prevent boiling within of the media vessel, under no flow conditions. A safety significant control, maintaining loadings less than the established loading limit ensures associated impacts to human health and the environment are prevented. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Impacts of control strategies, the Great Recession and weekday variations on NO 2 columns above North American cities

The Ozone Monitoring Instrument (OMI) has been estimating NO2 columns from space for over 10 years, and these have been used to estimate emissions and emission trends for point and area sources all over the world. In this study we evaluate the trends in NO2 columns over 54 cities in the USA and Canada to identify the long term trends due to air quality policies, the impact of the Great Recession, and the weekday-weekend effect. A multiple linear regression model is used to fit annual, seasonal and weekly factors for individual swath retrievals along with the impact of temperature, wind speed and pixel size. For most cities, the correlation coefficients of the model fit ranges from 0.47 to 0.76. There have been strong reductions in NO2 columns, with annual decreases of up to 7% per year in most cities. During the years of the Great Recession, NO2 columns were as much as 30% lower than they would have been had they followed the linear annual trend. The analysis yielded insights into the timing of the reductions, with some cities in the northwest and in the east experiencing reductions in 2008 already, and most areas back to where they would have been based on the uniform trend by 2011. The analysis also finds that reductions in columns during the weekend vary significantly from city to city, with a range in reductions of 10%-30% on Saturdays, and 20%-50% on Sundays.

de Foy, Benjamin (ORCID:0000000341509922)↗

Hydrate Formation on Marine Seep Bubbles and the Implications for Water Column Methane Dissolution

Abstract Methane released from seafloor seeps contributes to a number of benthic, water column, and atmospheric processes. At seafloor seeps within the methane hydrate stability zone, crystalline gas hydrate shells can form on methane bubbles while the bubbles are still in contact with the seafloor or as the bubbles begin ascending through the water column. These shells reduce methane dissolution rates, allowing hydrate‐coated bubbles to deliver methane to shallower depths in the water column than hydrate‐free bubbles. Here, we analyze seafloor videos from six deepwater seep sites associated with a diverse range of bubble‐release processes involving hydrate formation. Bubbles that grow rapidly are often hydrate‐free when released from the seafloor. As bubble growth slows and seafloor residence time increases, a hydrate coating can form on the bubble's gas‐water interface, fully coating most bubbles within ∼10 s of the onset of hydrate formation at the seafloor. This finding agrees with water‐column observations that most bubbles become hydrate‐coated after their initial ∼150 cm of rise, which takes about 10 s. Whether a bubble is coated or not at the seafloor affects how much methane a bubble contains and how quickly that methane dissolves during the bubble's rise through the water column. A simplified model shows that, after rising 150 cm above the seafloor, a bubble that grew a hydrate shell before releasing from the seafloor will have ∼5% more methane than a bubble of initial equal volume that did not grow a hydrate shell after it traveled to the same height.

54 ENVIRONMENTAL SCIENCES↗