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DOE OSTI2022

Consistent responses of vegetation gas exchange to elevated atmospheric CO 2 emerge from heuristic and optimization models

Elevated atmospheric CO 2 concentration is expected to increase leaf CO 2 assimilation rates, thus promoting plant growth and increasing leaf area. It also decreases stomatal conductance, allowing water savings, which have been hypothesized to drive large-scale greening, in particular in arid and semiarid climates. However, the increase in leaf area could reduce the benefits of elevated CO 2 concentration through soil water depletion. The net effect of elevated CO 2 on leaf- and canopy-level gas exchange remains uncertain. To address this question, we compare the outcomes of a heuristic model based on the Partitioning of Equilibrium Transpiration and Assimilation (PETA) hypothesis and three model variants based on stomatal optimization theory. Predicted relative changes in leaf- and canopy-level gas exchange rates are used as a metric of plant responses to changes in atmospheric CO 2 concentration. Both model approaches predict reductions in leaf-level transpiration rate due to decreased stomatal conductance under elevated CO 2 , but negligible (PETA) or no (optimization) changes in canopy-level transpiration due to the compensatory effect of increased leaf area. Leaf- and canopy-level CO 2 assimilation is predicted to increase, with an amplification of the CO 2 fertilization effect at the canopy level due to the enhanced leaf area. The expected increase in vapour pressure deficit (VPD) under warmer conditions is generally predicted to decrease the sensitivity of gas exchange to atmospheric CO 2 concentration in both models. The consistent predictions by different models that canopy-level transpiration varies little under elevated CO 2 due to combined stomatal conductance reduction and leaf area increase highlight the coordination of physiological and morphological characteristics in vegetation to maximize resource use (here water) under altered climatic conditions.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Long-Term 13 C Uptake by 12 C-Enriched Calcite

Knowledge of the exchange of carbon isotopes between dissolved inorganic carbon and calcite minerals is of long-standing importance for the interpretation of sedimentary paleoclimate records and 14 C transport in the geosphere. To assess the mechanism and rates of carbon isotope exchange, we equilibrated 12 C-pure synthetic calcite particles in water, first in a glovebox and then in contact with atmospheric P CO 2 and 13 C/ 12 C ratio, at two different temperatures. Cavity ring-down infrared spectroscopy δ 13 C measurements of the solid revealed sustained 13C incorporation for over a period of 500 days (21 °C) and 125 days (50 °C). We developed a quantitative model for recrystallization and isotope exchange, assuming that the interfacial free energy provides a thermodynamic driving force for the growth of larger particles at the expense of smaller ones. Furthermore, this Ostwald ripening model did not reproduce the kinetics of 13C uptake and required greater coarsening than observed. Rather, the data were best explained by a mechanism involving surface exchange and solid-phase diffusion of 13C into the particles with an inferred effective diffusion constant at 21 °C of about 10 –25 m 2 /s. Although this work cannot rule out the possibility that structural or chemical aspects of the synthetic particles enabled faster 13 C uptake than could be observed in natural systems, this study adds to the body of the recent work, suggesting that fast exchange processes are possible, likely through grain boundaries and other defects.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2012

Contaminant Removal from Oxygen Production Systems for In Situ Resource Utilization

The In Situ Resource Utilization (ISRU) project has been developing technologies to produce oxygen from lunar regolith to provide consumables to a lunar outpost. The processes developed reduce metal oxides in the regolith to produce water, which is then electrolyzed to produce oxygen. Hydrochloic and hydrofluoric acids are byproducts of the reduction processes, as halide minerals are also reduced at oxide reduction conditions. Because of the stringent water quality requirements for electrolysis, there is a need for a contaminant removal process. The Contaminant Removal from Oxygen Production Systems (CROPS) team has been developing a separation process to remove these contaminants in the gas and liquid phase that eliminates the need for consumables. CROPS has been using Nafion, a highly water selective polymeric proton exchange membrane, to recover pure water from the contaminated solution. Membrane thickness, product stream flow rate, and acid solution temperature and concentration were varied with the goal of maximizing water permeation and acid rejection. The results show that water permeation increases with increasing solution temperature and product stream flow rate, while acid rejection increases with decreasing solution temperature and concentration. Thinner membranes allowed for higher water flux and acid rejection than thicker ones. These results were used in the development of the hardware built for the most recent Mars ISRU demonstration project.

Anthony, Stephen M.↗

NASA NTRS2016

Recent Changes in Land Water Storage and Its Contribution to Sea Level Variations

Sea level rise is generally attributed to increased ocean heat content and increased rates glacier and ice melt. However, human transformations of Earth's surface have impacted water exchange between land, atmosphere, and ocean, ultimately affecting global sea level variations. Impoundment of water in reservoirs and artificial lakes has reduced the outflow of water to the sea, while river runoff has increased due to groundwater mining, wetland and endorheic lake storage losses, and deforestation. In addition, climate-driven changes in land water stores can have a large impact on global sea level variations over decadal timescales. Here, we review each component of negative and positive land water contribution separately in order to highlight and understand recent changes in land water contribution to sea level variations.

Reservoir impoundment↗

NASA NTRS2007

Space Suit Radiator Performance in Lunar and Mars Environments

During an ExtraVehicular Activity (EVA), both the heat generated by the astronaut's metabolism and that produced by the Portable Life Support System (PLSS) must be rejected to space. The heat sources include the heat of adsorption of metabolic CO2, the heat of condensation of water, the heat removed from the body by the liquid cooling garment and the load from the electrical components. Although the sublimator hardware to reject this load weighs only 3.48 lbs, an additional eight pounds of water are loaded into the unit of which about six to eight are sublimated and lost; this is the single largest expendable during an eight-hour EVA. Using a radiator to reject heat from the Astronaut during an EVA, we can significantly reduce the amount of expendable water consumed by the sublimator. Last year we reported on the design and initial operational assessment tests of our novel radiator designated the Radiator And Freeze Tolerant heat eXchanger (RAFT-X). Herein, we report on tests conducted in the NASA Johnson Space Center Chamber E Thermal Vacuum Test Facility. Up to 800 Btu/h of heat were rejected in lunar and Mars environments with temperatures as cold as 150 F. Tilting the radiator did not cause an observable loss in performance. The RAFT-X endured freeze/thaw cycles and in fact, the heat exchanger was completely frozen three times without any apparent damage to the unit. We were also able to operate the heat exchanger in a partially frozen configuration to throttle the heat rejection rate from 530 Btu/h at low water flow rate down to 300 Btu/h. Finally, the deliberate loss of a single loop heat pipe only degraded the heat rejection performance by about 2 to 5%.

Paul, Heather↗

NASA NTRS2007

Space Suit Radiator Performance in Lunar and Mars Environments

During an ExtraVehicular Activity (EVA), both the heat generated by the astronaut's metabolism and that produced by the Portable Life Support System (PLSS) must be rejected to space. The heat sources include the heat of adsorption of metabolic CO2, the heat of condensation of water, the heat removed from the body by the liquid cooling garment and the load from the electrical components. Although the sublimator hardware to reject this load weighs only 3.48 lbs, an additional eight pounds of water are loaded into the unit of which about six to eight are sublimated and lost; this is the single largest expendable during an eight-hour EVA. Using a radiator to reject heat from the Astronaut during an EVA, we can significantly reduce the amount of expendable water consumed by the sublimator. Last year we reported on the design and initial operational assessment tests of our novel radiator designated the Radiator And Freeze Tolerant heat eXchanger (RAFT-X). Herein, we report on tests conducted in the NASA Johnson Space Center Chamber E Thermal Vacuum Test Facility. Up to 800 Btu/h of heat were rejected in lunar and Mars environments with temperatures as cold as -150 F. Tilting the radiator did not cause an observable loss in performance. The RAFT-X endured freeze / thaw cycles and in fact, the heat exchanger was completely frozen three times without any apparent damage to the unit. We were also able to operate the heat exchanger in a partially frozen configuration to throttle the heat rejection rate from 530 Btu/h at low water flow rate down to 300 Btu/h. Finally, the deliberate loss of a single loop heat pipe only degraded the heat rejection performance by about 2 to 5%.

Nabity, James↗

DOE OSTI2023

Analysis of bipolar membranes for electrochemical CO 2 capture from air and oceanwater

Carbon dioxide (CO 2 ) must be removed from the atmosphere to mitigate the negative effects of climate change. However, the most scalable methods for removing CO 2 from the air require heat from fossil-fuel combustion to produce pure CO 2 and continuously regenerate the sorbent. Bipolar-membrane electrodialysis (BPM-ED) is a promising technology that uses renewable electricity to dissociate water into acid and base to regenerate bicarbonate-based CO 2 capture solutions, such as those used in chemical loops of direct-air-capture (DAC) processes, and in direct-ocean capture (DOC) to promote atmospheric CO 2 drawdown via decarbonization of the shallow ocean. In this study, we develop an experimentally validated 1D model for the electrochemical regeneration of CO 2 from bicarbonate-based carbon capture solutions and seawater using BPM-ED. For DAC, our experimental and computational results demonstrate that pH swings induced by BPM water dissociation drive the formation of CO 2 at the cation-exchange layer|catholyte interface with energy-intensities of less than 150 kJ mol -1 . However, high rates of bubble formation increase energy intensity at current densities >100 mA cm -2 . Correspondingly, accelerating water dissociation catalysis and enacting bubble removal could enable CO 2 recovery at energy intensities <100 kJ mol -1 and current densities >100 mA cm -2 . For DOC, mass transport limitations associated with low carbon concentrations in oceanwater suggest that DOC is best suited for clean production of acid and base usable in downstream processes. Further, these results provide design principles for industrial-scale CO 2 recovery using BPM-ED.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

An experimental study on dehumidification and regeneration performance of a new nonporous membrane-based heat and mass exchanger using an ionic liquid desiccant

As a promising alternative to inefficient vapor-compression-based air conditioning, liquid desiccant dehumidification uses a liquid desiccant in contact with the humid air absorbing the moisture. However, it has not gained much market share due to the issues related to the carryover, corrosion, fouling, and crystallization of liquid desiccant. The research has developed a new membrane-based exchanger, which uses a non-corrosive ionic liquid desiccant and nonporous tubular membranes to address these issues. As the second generation of the prototype, the new exchanger was tested at various operating conditions. According to the experimental data, when it is used in the dehumidification loop, the new membrane-based exchanger achieves a specific vapor transportation rate of 778.6 g/(h–m 2 ) and an average water vapor flux of 0.316 g/(h-m 2 -Pa), which is a significant improvement compared with the previous designs using nonporous membranes. It also achieved a comparable or even better dehumidification performance compared with the dehumidifiers that use porous membrane and conventional liquid desiccants. However, the regeneration performance is not as good as its dehumidification. It is mainly caused by the high operating temperature required in the regeneration loop. The experimental data and findings provide first-hand experimental data and enhance the understanding of advanced membrane-based ionic liquid desiccant systems.

42 ENGINEERING↗

DOE OSTI2020

Insights into the Water Transport Mechanism in Polymeric Membranes from Neutron Scattering

Polymeric membranes are ubiquitous in transport applications including gas separation, water desalination, solid-state batteries, and fuel cells. The transport mechanism in certain classes of membranes is well understood. It is generally believed that polymeric membranes used in gas separation follow the solution-diffusion model. However, the transport mechanism in other membranes such as the ones used in water desalination is less clear as both the solution-diffusion and hydrodynamic models have been proposed. In this contribution, we study the structure as well as the water and polymer dynamics of several polymeric membranes using small-angle and quasi-elastic neutron scattering. We demonstrate that on the scale of a few nanometers, water appears to diffuse through a desalination membrane at a rate comparable to bulk water, while water diffuses at a rate that is a factor of 2 slower in an anion-exchange membrane. These results illustrate the importance of studying both the structure and dynamics of membrane materials and have important implications in understanding the transport mechanisms that differentiate the different types of polymeric membranes.

36 MATERIALS SCIENCE↗

DOE OSTI2024

The Influence of Air‐Sea CO 2 Disequilibrium on Carbon Sequestration by the Ocean's Biological Pump

Abstract The ocean's biological carbon pump (BCP) affects the Earth's climate by sequestering CO 2 away from the atmosphere for decades to millennia. One primary control on the amount of carbon sequestered by the biological pump is air‐sea CO 2 disequilibrium, which is controlled by the rate of air‐sea CO 2 exchange and the residence time of CO 2 in surface waters. Here, we use a data‐assimilated model of the soft tissue BCP to quantify carbon sequestration inventories and time scales from remineralization in the water column to equilibration with the atmosphere. We find that air‐sea CO 2 disequilibrium enhances the global biogenic carbon inventory by ∼35% and its sequestration time by ∼70 years compared to identical calculations made assuming instantaneous air‐sea CO 2 exchange. Locally, the greatest enhancement occurs in the subpolar Southern Ocean, where air‐sea disequilibrium increases sequestration times by up to 600 years and the biogenic dissolved inorganic carbon inventory by >100% in the upper ocean. Contrastingly, in deep‐water formation regions of the North Atlantic and Antarctic margins, where biological production creates undersaturated surface waters which are subducted before fully equilibrating with the atmosphere, air‐sea CO 2 disequilibrium decreases the depth‐integrated sequestration inventory by up to ∼150%. The global enhancement of carbon sequestration by air‐sea disequilibrium is particularly important for carbon respired in deep waters that upwell in the Southern Ocean. These results highlight the importance of accounting for air‐sea CO 2 disequilibrium when evaluating carbon sequestration by the biological pump and for assessing the efficacy of ocean‐based CO 2 removal methods.

Environmental Sciences & Ecology↗

NASA NTRS1970

The water-cryogen heat exchanger

Heat exchanger, using water as heat medium, converts liquid hydrogen to gaseous hydrogen at a very high rate. Possible applications include treatment of liquified natural gas in cities to bring the gas on-line quickly, conversion of liquid oxygen and liquid nitrogen for steel mills, and high volume inert purging.

Bartlit, J. R.↗

NASA NTRS2021

On the Cycling of 231 Pa and 230 Th in Benthic Nepheloid Layers

The naturally-occurring radionuclides protactinium-231 ( 231 Pa) and thorium-230 ( 230 Th) are produced at approximately uniform rates in the ocean and thought to be removed from the water column through a reversible exchange with settling particles. Recent measurements along the U.S. GEOTRACES North Atlantic transect (GA03) revealed two features which are at odds with current understanding about 231 Pa and 230 Th cycling in the ocean: (i) a sharp decrease in dissolved 231 Pa ( 231 Pa d ) and 230 Th ( 230 Th d ) activities with depth below 2000-4000 m and (ii) very high particulate 231 Pa ( 231 Pa p ) and 230 Th ( 230 Th p ) activities near the bottom, at a number of stations between the New England continental shelf and Bermuda. Concomitant measurements of light attenuation from beam transmissometry showed that both features occur in benthic nepheloid layers (BNLs), which suggests that these features may stem, at least partly, from the presence of resuspended sediment in the deep water column. Here we explore the behaviour of 231 Pa and 230 Th in BNLs by using (i) radionuclide, optical, and hydrographic data from the western segment of GA03 (west of Bermuda) and (ii) a simplified model of particle and radionuclide cycling that includes a lateral particle source. First, the BNLs observed at GA03 stations are characterized from measurements of the beam attenuation coefficient converted to particle concentrations. At all stations, particle concentrations below the clear water minimum were the highest in the bottom mixed layer, whose thickness ranged from 95 to 320 m, and decreased generally with height above the bottom. The thickness of strong BNLs varied from 482 to 1358 m and the vertical integral of particle concentration in excess to that at the clear water minimum varied from 1 x 10 4 to 2 x 10 6 mg m −2 , among different stations. Second, the particle-radionuclide model is fitted to data from stations GT11-04 (New England continental rise) and GT11-08 (Hatteras abyssal plain), where samples for radionuclide analyses were collected in the BNL. The model can reproduce simultaneously the increase of particle concentration with depth, the low 231 Pa d and 230 Th d in the BNLs, and the high 231 Pa p and 230 Th p near the bottom. According to the model, at heights less than about 300 m above the seafloor, the dissolved phase was set primarily by a balance between adsorption and desorption, with vertical turbulent mixing playing a secondary role, whilst the particulate phase behaved largely as a non-reactive constituent supplied laterally and transported vertically by particle settling and turbulent mixing. Sensitivity tests with the model suggest that lateral particle sources near continental slopes and similar reliefs can produce significant biases both in the 230 Th normalization method and in the interpretation of sediment 231 Pa/ 230 Th records. Our findings yield insights into the influence of sediment resuspension and transport on 231 Pa and 230 Th in the deep ocean and highlight the need for considering these processes in paleoceanographic applications.

Nepheloid layer↗

NASA NTRS1994

Exchange of nitrous oxide within the Hudson Bay lowland

The source strength of atmospheric trace gases from natural ecosystems must be quantified in order to assess the effect of such inputs on the background tropospheric chemistry. A static chamber technique and a gas exchange technique were used to determine the emissions of nitrous oxide from five sites within the Hudson Bay Lowland, as part of the Northern Wetland Study. Two mechanisms, one diffusive and the other episodic, were found likely to be responsible for the emissions of nitrous oxide. The annual diffusive flux ranged from -3.8 mg(N2O)/sq m in a treed bog to 7.9 mg(N2O)/sq m in an open fen. The addition of the episodic flux, increased this range to -2.1 mg(N2O)/sq m and 18.5 mg(N2O)/sq m respectively. These episodic emissions occurred in from 2.5% to 16.7% of the samples during the late summer peak emission period. Since the gas exchange rate could not detect the episodic emissions, it was found to be a poor method for water emission rate determination within the wetland. LANDSAT-Thermatic Mapper (TM) imagery was used to scale the emissions, from the chamber level to an integrated average over the entire Hudson Bay Lowland. The total emission rate of N2O from the Hudson Bay Lowland, was determined to be 1.2 Gg(N2O)/year, of which 80% was attributed to episodic emissions.

Schiller, C. L.↗

NASA NTRS2003

Earth System Dynamics: The Determination and Interpretation of the Global Angular Momentum Budget using the Earth Observing System

The objective of this investigation has been to examine the mass and momentum exchange between the atmosphere, oceans, solid Earth, hydrosphere, and cryosphere. The investigation has focused on changes in the Earth's gravity field, its rotation rate, atmospheric and oceanic circulation, global sea level change, ice sheet change, and global ground water circulation observed by contemporary sensors and models. The primary component of the mass exchange is water. The geodetic observables provided by these satellite sensors are used to study the transport of water mass in the hydrological cycle from one component of the Earth to another, and they are also used to evaluate the accuracy of models. As such, the investigation is concerned with the overall global water cycle. This report provides a description of scientific, educational and programmatic activities conducted during the period July 1, 1999 through June 30,2000. Research has continued into measurements of time-varying gravity and its relationship to Earth rotation. Variability of angular momentum and the related excitation of polar motion and Earth rotation have been examined for the atmosphere and oceans at time-scales of weeks to several years. To assess the performance of hydrologic models, we have compared geodetic signals derived from them with those observed by satellites. One key component is the interannual mass variability of the oceans obtained by direct observations from altimetry after removing steric signals. Further studies have been conducted on the steric model to quantify its accuracy at global and basin-scales. The results suggest a significant loss of water mass from the Oceans to the land on time-scales longer than 1-year. These signals are not reproduced in any of the models, which have poorly determined interannual fresh water fluxes. Output from a coupled atmosphere-ocean model testing long-term climate change hypotheses has been compared to simulated errors from the Gravity Recovery and Climate Experiment (GRACE) mission. Results indicate that GRACE will be able to observe seasonal signals at half-wavelengths ranging from 1000 to 10000 km, and may be able to observe secular trends at half- wavelengths of greater than 2000-3000 km for soil moisture and snow depth if they are as large as some of the climate experiments predict.

Source record↗

DOE OSTI2025

Experimental investigation on heat transfer performance of drain water heat recovery heat exchangers

Water heating accounts for 18 % of residential energy consumption, and a substantial portion of this energy can be recovered through drain water heat recovery systems. Here, this paper investigates the heat transfer performance of drain water heat recovery heat exchangers. Two heat exchanger configurations were studied: vertical (gravity film exchanger) and horizontal. The heat recovery performance of the exchangers was quantified using sensible effectiveness and characteristic curves following the ε-NTU approach. Depending on the flow conditions, heat exchangers with a vertical configuration offered higher heat transfer effectiveness compared with the horizontal configuration under similar operating conditions. Furthermore, the results showed that properly designed and sized heat exchangers can effectively recover considerable amounts of waste heat from drains, depending on flow rates. Additionally, in the vertical heat exchanger configuration, low flow rates result in partially wet conditions, resulting in lower heat transfer effectiveness. Therefore, two distributor configurations are proposed to improve the heat transfer performance of vertically configured heat exchangers at low flow rates. The proposed distributor configurations and data presented in this paper will be useful in the design and development of drain water heat recovery systems in building applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2024

Exploring CO 2 reduction and crossover in membrane electrode assemblies

Electrochemical CO 2 reduction (CO 2 R) using renewable electricity is a key pathway toward synthesizing fuels and chemicals. In this study, multi-physics modeling is used to interpret experimental data obtained for CO 2 R to CO using Ag catalysts in a membrane electrode assembly. The one-dimensional model is validated using measured CO 2 crossover and product formation rates. The kinetics of CO formation are described by Marcus–Hush–Chidsey kinetics, which enables accurate prediction of the experimental data by accounting for the reorganization of the solvent during CO 2 R. Further, the results show how the performance is dictated by competing phenomena including ion formation and transport, CO 2 solubility, and water management. The model shows that increasing the ion-exchange capacity of the membrane and surface area of the catalyst increases CO formation rates by >100 mA cm –2 without negatively impacting CO 2 utilization. Here we provide insights into how to manage the trade-off between productivity and CO 2 utilization in CO 2 electrolyzers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2004

Properties of a Novel Ion-Exchange Film

A new ion-exchange material (based on polyacrylic acid) and some of its analytical applications have been reported. This paper contains data on the ion-exchange properties of the film form of the material and its potential application to the decontamination of waste water and drinking water. The film has a high exchange capacity of 5 to 6 meq/g and a pK(sub a) of 5.7. The calcium form is the most effective for removing metal ions from solution, and the optimum pH range is between 5 and 7. The exchange rates are slower for the film than for bead and powder forms of the ion-exchange material; otherwise, the properties are similar. The film is effective when hard water solutions are employed and also when metal ions are in the complex matrix of waste water from electroplating. The film can be used in flow systems having a flow channel large enough to allow passage of turbid solutions.

Street, Kenneth W.↗

NASA NTRS2002

Properties of a Novel Ion-Exchange Film

Street, Kenneth W.↗