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At least 19 records

Carbon dioxide and water exchange rates by a wheat crop in NASA's biomass production chamber: Results from an 86-day study (January to April 1989)

Gas exchange measurements were taken for a 20 sq m wheat stand grown from seed to harvest in NASA's Biomass Production Chamber. Respiration of the wheat stand caused the CO2 concentrations to rise an average of 440 ppm during the 4-h dark period each day, or 7.2 umol/sq m/sec. Dark period respiration was sensitive to temperature changes and could be increased 70 to 75 percent by raising the temperature from 16 C to 24 C. Stand photosynthesis (measured from the rate of CO2 drawdown immediately after the lights came on each day) peaked at 27 umol/sq m/sec at 25 days after planting and averaged 15 umol/sq m/sec throughout the study. By combining the average light period photosynthesis and average dark period respiration, a net of 860 g or 470 liters of CO2 were fixed per day. Stand photosynthetic rates showed a linear increase with increasing irradiance (750 umol/sq m/sec PPF the highest level tested), with an average light compensation point after day 30 of 190 umol/sq m/sec. Stand photosynthesis decreased slightly when CO2 levels were decreased from 2200 to 800 ppm, but dropped sharply when CO2 was decreased below 700 to 800 ppm. Water production from stand transpiration peaked at 120 L/day near 25 days and averaged about 90 L/day, or 4.5 L/sq m/day throughout the study.

Wheeler, R. M.↗

High resolution identification and quantification of diffuse deep groundwater discharge in mountain rivers using continuous boat-mounted helium measurements

Discharge of deeply sourced groundwater to streams is difficult to locate and quantify, particularly where both discrete and diffuse discharge points exist, but diffuse discharge is one of the primary controls on solute budgets in mountainous watersheds. The noble gas helium is a unique identifier of deep groundwater discharge because groundwater with long residence times is commonly enriched in helium. In this study, a portable mass spectrometer was used to measure longitudinal variation in dissolved helium concentrations in two mountainous rivers at high spatial resolution not feasible with traditional sampling techniques. Helium profiles were then simulated using a mass-balance model to quantify longitudinal variation in groundwater discharge to the receiving rivers. Results indicate helium concentrations were enriched by multiple orders of magnitude above atmospheric equilibrium in both rivers and that this persisted for up to 18 km below observed pulse inputs in the Colorado River. Helium mass-balance models match observed longitudinal patterns with the exception of sharp initial increases in helium observed in the rivers. Increased longitudinal groundwater discharge rates correspond to mapped geologic structures in both watersheds that likely transport deep geothermal water. Models show variable sensitivity to spatial assignment of input variables representing the groundwater source, illustrating the importance of collecting data from discrete groundwater discharges where possible. The methodology shows promise for field experiments designed to assess air–water exchange rates and to quantify total groundwater discharge from a combination of discrete and diffuse sources.

Deep groundwater↗

Nickel hydroxide–nickel carbonate competitive growth on carbonate surfaces

The thermodynamic and kinetic factors controlling the competitive heterogeneous nucleation and growth of ubiquitous metal carbonate and hydroxide phases are poorly understood. In this work, calcite (CaCO 3 ) and magnesite (MgCO 3 ) powders were reacted with NiCl 2 (0–600 μM) for 7 days at 22 °C and 5 °C. The reacted powders were analyzed with X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, and energy-dispersive X-ray spectroscopy to characterize the Ni surface precipitates formed. Evidence from these techniques pointed to the formation of mixed Ni carbonate-Ni hydroxide amorphous surface precipitates. On calcite, XPS detected primarily Ni(OH) 2 despite the initial solutions being more supersaturated with respect to gaspéite (NiCO 3 ) than to theophrastite (Ni(OH) 2 ) by a factor of 17–18. In contrast, NiCO 3 was the dominant component detected by XPS on magnesite in the same conditions. Decreasing the temperature had the effect of increasing the proportion of NiCO 3 to the detriment of Ni(OH) 2 . The experimental observations were consistent with low lattice/cation size mismatch favoring NiCO 3 nucleation and temperature most influencing Ni(OH) 2 nucleation. Comparison to previous work on Co-reacted powders indicated the differences in lattice/cation size mismatch and/or water exchange rate impacted the composition of the surface precipitates more than the relative thermodynamic stabilities of the competing minerals. This work explored the heterogeneous growth regime of Ni carbonate and hydroxide phases on carbonate surfaces and shed light on the factors that control the competition between surface precipitates when mineral surfaces are in contact with aqueous solutions supersaturated with respect to multiple mineral phases. In conclusion, these results contribute to geochemists’ efforts toward interpreting data from geochemical systems with elevated Ni concentrations, improving Ni environmental remediation and recovery strategies, and predicting the fate and transport of Ni in geochemical systems.

Heterogeneous nucleation↗

System development and early biological tests in NASA's biomass production chamber

The Biomass Production Chamber at Kennedy Space Center was constructed to conduct large scale plant growth studies for NASA's CELSS program. Over the past four years, physical systems and computer control software have been continually upgraded and the degree of atmospheric leakage from the chamber has decreased from about 40 to 5 percent of the total volume per day. Early tests conducted with a limited degree of closure showed that total crop (wheat) growth from the best trays was within 80 percent of reported optimal yields for similar light levels. Yields from subsequent tests under more tightly closed conditions have not been as good--up to only 65 percent of optimal yields. Yields appear to have decreased with increasing closure, yet potential problems exist in cultural techniques and further studies are warranted. With the ability to tightly seal the chamber, quantitative data were gathered on CO2 and water exchange rates. Results showed that stand photosynthesis and transpiration reached a peak near 25 days after planting, soon after full vegetative ground cover was established. In the final phase of testing when atmospheric closure was the highest, ethylene gas levels in the chamber rose from about 10 to nearly 120 ppb. Evidence suggests that the ethylene originated from the wheat plants themselves and may have caused an epinastic rolling of the leaves, but no apparent detrimental effects on whole plant function.

Wheeler, R. M.↗

Stable Isotope Characteristics of Jarosite: The Acidic Aqueous History of Mars

The Mars Rover Opportunity found jarosite (Na(+) or K(+))Fe3SO4(OH)6 at the Meridiani Planum site. This mineral forms from the evaporation of an aqueous acidic sulfate brine. Oxygen isotope compositions may characterize formation conditions but subsequent isotope exchange may have occurred between the sulfate and hydroxide of jarosite and water. The rate of oxygen isotope exchange depends on the acidity and temperature of the brine, but it has not been investigated in detail. We performed laboratory experiments to determine the rate of oxygen isotope exchange under varying acidities and temperatures to learn more about this process. Barium sulfate samples were precipitated weekly from acidic sodium sulfate brines. The oxygen isotope composition of the precipitated sulfate was obtained using a Finnigan MAT253 Isotope Ratio Mass-Spectrometer. The results show that water was trapped in barium sulfate during precipitation. Trapped water may exchange with sulfate when exposed to high temperatures, thus changing the isotope composition of sulfate and the observed fractionation factor of oxygen isotope exchange between sulfate and water. The results of our research will contribute to the understanding of oxygen isotope exchange rates between water and sulfate under acidic conditions and provide experimental knowledge for the dehydration of barium sulfate samples.

Earl, Lyndsey D.↗

A GCM Recent History of the Northern Martian Polar Layered Deposits

The polar layered deposits are thought to contain alternate layers of water and dust in different proportions resulting from the astronomical forcing of the martian climate. In particular, longterm variations in the orbital and axial elements of Mars are presumed to generate variations of the latitudes of surface water ice stability and of the amount of water exchanged in the polar areas. At high obliquity, simplified climate models and independent general circulation simulations suggest a transfer of water ice from the north polar region to tropical areas, whereas at lower and present obliquities, water ice is expected to be stable only at the poles. If so, over obliquity cycles, water ice may be redistributed between the surface water reservoirs leading to their incremental building or disintegration depending on the rates of water transfer. If only a relative limited amount of the available water is exchanged on orbital timescales, this may provide an efficient mechanism for the formation of the observed polar deposits. Within this context, GCM simulations of the martian water cycle have been performed for various obliquities ranging from 15 degrees to 45 degrees and for a large set of initial water ice locations to determine the rate of water exchange between the surface water reservoirs as a function of the obliquity. Propagating these rates over the last 10 Ma orbital history gives a possible recent evolution of these reservoirs.

Levrard, B.↗

Hyporheic hydraulic geometry: Conceptualizing relationships among hyporheic exchange, storage, and water age

Hyporheic exchange is now widely acknowledged as a key driver of ecosystem processes in many streams. Yet stream ecologists have been slow to adopt nuanced hydrologic frameworks developed and applied by engineers and hydrologists to describe the relationship between water storage, water age, and water balance in finite hydrosystems such as hyporheic zones. Here, in the context of hyporheic hydrology, we summarize a well-established mathematical framework useful for describing hyporheic hydrology, while also applying the framework heuristically to visualize the relationships between water age, rates of hyporheic exchange, and water volume within hyporheic zones. Building on this heuristic application, we discuss how improved accuracy in the conceptualization of hyporheic exchange can yield a deeper understanding of the role of the hyporheic zone in stream ecosystems. Although the equations presented here have been well-described for decades, our aim is to make the mathematical basis as accessible as possible and to encourage broader understanding among aquatic ecologists of the implications of tailed age distributions commonly observed in water discharged from and stored within hyporheic zones. Our quantitative description of “hyporheic hydraulic geometry,” associated visualizations, and discussion offer a nuanced and realistic understanding of hyporheic hydrology to aid in considering hyporheic exchange in the context of river and stream ecosystem science and management.

54 ENVIRONMENTAL SCIENCES↗

Mass, heat and freshwater fluxes in the South Indian Ocean

Six hydrographic sections were used to examine the circulation and property fluxes in the South Indian Ocean from 10 to 32 deg S. The calculations were made by applying an inverse method to the data. In the interior of the South Indian Ocean, the geostrophic flow is generally northward. At 18 deg S, the northward interior mass flux is balanced by the southward Ekman mass flux at the surface, whereas at 32 deg S the northward interior mass flux is balanced by the southward mass flux of the Agulhas Current. There is a weak, southward mass flux of 6 x 10 to the 9th kg/s in the Mozambique Channel. The rate of water exchange between the Pacific Ocean and the Indian Ocean is dependent on the choice of the initial reference level used in the inverse calculation. The choice of 1500 m, the depth of the deep oxygen minimum, has led to a flux of water from the Pacific Ocean to the Indian Ocean at a rate of 6.6 x 10 to the 9th kg/s. Heat flux calculations indicate that the Indian Ocean is exporting heat to the rest of the world's oceans at a rate of -0.69 x 10 to the 15th W at 18 deg S and -0.25 x 10 to the 15th W at 32 deg S (negative values being southward).

Fu, Lee-Lueng↗

Organophosphorus Binding Thermodynamics in Metal–Organic Frameworks: Interplay between Oxidation State, Lewis Acidity, and Node Structure

Organophosphorus compounds, including nerve agents and pesticides, represent a class of toxic chemicals causing harm to troops, civilians, and the environment. Metal–organic frameworks (MOFs) have emerged as a class of highly porous, crystalline, tunable materials adept at both capturing and catalytically neutralizing these harmful toxins. In particular, MOFs whose nodes display strong Lewis acidic character can hydrolyze such chemicals nearly instantaneously. However, without the help of a basic buffer to regenerate the active site, the benign organophosphorus product strongly binds to the node and prevents catalyst turnover. Here, we investigate a series of MOFs whose nodes contain metals of varying Lewis acidities and employ isothermal titration calorimetry (ITC) to directly measure the heat from the binding of an organophosphorus probe molecule, allowing the construction of a full thermodynamic binding profile (ΔH, ΔS, ΔG, K a ). We couple this with potentiometric titrations and solid state 31 P magic angle spinning (MAS) NMR to gain a clearer picture of how node identity, structure, and Lewis acidity interplay to impact binding strength and favorability. Furthermore, this study is the first to integrate these three complementary techniques to investigate binding interactions in MOFs, further showcasing the viability of ITC for probing MOF systems, which is still relatively underexplored.

Lewis acidity↗

Diffusion and Solvation Dynamics of Ions in Water: Beyond the Brownian Approximation

The coupled dynamics of ions and water molecules in their first hydration shell impact a variety of processes including ion diffusion, selective ion transport in water-filled nanopores, and the kinetics of ion-pairing, ion adsorption, and metal-ligand binding reactions. In this work, we study these coupled dynamics for alkali metals (Li, Na, K, Rb, Cs), alkaline Earth metals (Mg, Ca, Sr, Ba), and chloride through the lens of their dependence on ion isotopic mass. Results are validated against previous measurements of the isotopic mass-dependence of ion diffusion coefficients in water and previous ab initio calculations of ion high-frequency dynamics in water. We find that the vibrational power spectra of ions in water consistently exhibit either two or three peaks, i.e., ions have several rattling frequencies within their solvations shells as previously reported for a subset of the species examined here. These frequencies have different sensititivies to isotopic mass that may serve as signatures of ion solvation processes (such as the tendency of ions to orient their first-shell water molecules) and that also may relate to Hofmeister-like effects including the relative affinity of different metals for ribonucleic acid (RNA).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radiation-induced D/H Exchange Rate Constants in Aliphatics Embedded in Water Ice

Gas-phase and solid-state chemistry in low-temperature interstellar clouds and cores leads to a D/H enhancement in interstellar ices, which is eventually inherited by comets, meteorites, and even planetary satellites. Hence, the D/H ratio has been widely used as a tracer for the origins of extraterrestrial chemistry. However, the D/H ratio can also be influenced by cosmic rays, which are ubiquitous and can penetrate even dense interstellar molecular cores. The effects of such high-energy radiation on deuterium fractionation have not been studied in a quantitative manner. In this study, we present rate constants for radiation-induced D-to-H exchange for fully deuterated small (1–2 C) hydrocarbons embedded in H2O ice at 20 K and H-to-D exchange for the protiated forms of these molecules in D2O ice at 20 K. We observed larger rate constants for H-to-D exchange in the D2O ice versus D-to-H exchange in H2O ice, which we have attributed to the greater bond strength of C–D versus C–H. We find that the H-to-D exchange rate constants are smaller for protiated methane than ethane, in agreement with bond energies from the literature. We are unable to obtain rate constants for the unsaturated and reactive hydrocarbons ethylene and acetylene. Interpretation of the rate constants suggest that D/H exchange products are formed in abundance alongside radiolysis products. We discuss how our quantitative and qualitative data can be used to interpret the D/H ratios of aliphatic compounds observed throughout space.

Ice destruction↗

Electrothermal mineralization of per- and polyfluoroalkyl substances for soil remediation

Abstract Per- and polyfluoroalkyl substances (PFAS) are persistent and bioaccumulative pollutants that can easily accumulate in soil, posing a threat to environment and human health. Current PFAS degradation processes often suffer from low efficiency, high energy and water consumption, or lack of generality. Here, we develop a rapid electrothermal mineralization (REM) process to remediate PFAS-contaminated soil. With environmentally compatible biochar as the conductive additive, the soil temperature increases to >1000 °C within seconds by current pulse input, converting PFAS to calcium fluoride with inherent calcium compounds in soil. This process is applicable for remediating various PFAS contaminants in soil, with high removal efficiencies ( >99%) and mineralization ratios ( >90%). While retaining soil particle size, composition, water infiltration rate, and cation exchange capacity, REM facilitates an increase of exchangeable nutrient supply and arthropod survival in soil, rendering it superior to the time-consuming calcination approach that severely degrades soil properties. REM is scaled up to remediate soil at two kilograms per batch and promising for large-scale, on-site soil remediation. Life-cycle assessment and techno-economic analysis demonstrate REM as an environmentally friendly and economic process, with a significant reduction of energy consumption, greenhouse gas emission, water consumption, and operation cost, when compared to existing soil remediation practices.

Science & Technology - Other Topics↗

The Effect of Rain on Air-Water Gas Exchange

The relationship between gas transfer velocity and rain rate was investigated at NASA's Rain-Sea Interaction Facility (RSIF) using several SF, evasion experiments. During each experiment, a water tank below the rain simulator was supersaturated with SF6, a synthetic gas, and the gas transfer velocities were calculated from the measured decrease in SF6 concentration with time. The results from experiments with IS different rain rates (7 to 10 mm/h) and 1 of 2 drop sizes (2.8 or 4.2 mm diameter) confirm a significant and systematic enhancement of air-water gas exchange by rainfall. The gas transfer velocities derived from our experiment were related to the kinetic energy flux calculated from the rain rate and drop size. The relationship obtained for mono-dropsize rain at the RSIF was extrapolated to natural rain using the kinetic energy flux of natural rain calculated from the Marshall-Palmer raindrop size distribution. Results of laboratory experiments at RSIF were compared to field observations made during a tropical rainstorm in Miami, Florida and show good agreement between laboratory and field data.

Ho, David T.↗

Ecosystem Modeling of Biological Processes to Global Budgets

From an ecological perspective, the search for life on distant planets begins from several key assumptions. The first of these is that, viewed from a remote location in space, the signature of life on a distant planet will be the result of net gas exchange of organisms with their environment. On the basis of extensive biogeochemical measurements and biogenic trace gas fluxes in modem Earth environments, it is probable that certain groups of organisms both produce and consume the same trace gas(es) within a single bioprofile of Solid (porous) substrate or surface water. The net gas exchange rate with the atmosphere measured at the living surface is frequently the result of competing metabolic reactions, which may carried out by different functional groups of organisms located at dissimilar 'climatic' or chemical microsites within the same bioprofile. Biogenic gases produced at one (deep) level of a bioprofile may be consumed by another functional group of organisms located closer to the level of surface exchange with the atmosphere. A second key assumption is that the net biogenic fluxes of atmospheric gases on Earth can be used to infer relative abundance and functional composition of the major organisms on a distant planet. Examples of this principle include the presence of methanogenic microorganisms abundant today in freshwater ecosystems worldwide, which are major source of atmospheric methane and its seasonal variability in Earth's atmosphere. A third assumption is that scaling up biogenic gas fluxes from a single biological community to the planetary level requires flux measurements at the whole ecosystem level. This implies that measurements of biogenic gas exchange with the global atmosphere cannot be easily inferred from measurements of gas production rates of single organisms, which may have been isolated in some manner from the setting of their native ecosystem. Hence, the unit of biological organization used in modern Earth Science for scaling up to biosphere effects on atmospheric composition is the ecosystem level. These assumptions are the foundation for developing modern emission budgets for biogenic gases such as carbon dioxide, methane, carbon monoxide, isoprene, nitrous and nitric oxide, and ammonia. Such emission budgets commonly include information on seasonal flux patterns, typical diurnal profiles, and spatial resolution of at least one degree latitude/longitude for the globe. On the basis of these budgets, it is possible to compute 'base emission rates' for the major biogenic trace gases from both terrestrial and ocean sources, which may be useful benchmarks for defining the gas production rates of organisms, especially those from early Earth history, which are required to generate a detectable signal on a global atmosphere. This type of analysis is also the starting point for evaluation of the 'biological processes to global gas budget' extrapolation procedure described above for early Earth ecosystems.

Christopher, Potter S.↗

River–aquifer interactions enhancing evapotranspiration in a semiarid riparian zone: A modelling study

The hydrologic flows across the river–aquifer interface play an important role in groundwater dynamics and biogeochemical reactions within the subsurface; however, little is known about the effects of river–aquifer interactions on land surface processes. In this study, we developed a fully coupled three-dimensional (3D) land surface and subsurface model at a high resolution (~1 km) that accounts for high-frequency hydrologic exchange flow conditions to investigate how river–aquifer interactions modulate surface water budgets in the Upper Columbia-Priest Rapids watershed, a typical semiarid watershed located in the northwestern United States where river stage fluctuates in response to reservoir releases changing. Our results show that the spatiotemporal dynamics of river–aquifer interactions are highly heterogeneous, driven mainly by river-stage fluctuations. Adding 6.64 × 10 6 m 3 year –1 of water over the watershed from the river to groundwater owing to the lateral flow, river–aquifer interactions led to an increase in soil evaporation and transpiration supplied by higher soil moisture content, particularly in deeper subsurface. In a hypothetic future scenarios where a 5-m rise in river stage was assumed, the hydrologic flow exchange rates were intensified, resulting in higher surface water over the entire watershed. Overall, lateral flow induced by river–aquifer exchanges leads to an increase in evapotranspiration of ~75% in the historical period and of ~83% in the hypothetical future scenario. Finally, our study demonstrates the potential of coupled model as an effective tool for understanding river–aquifer–land surface interactions, and indicates that river–aquifer interactions fundamentally alter the water balance of the riparian zone for the semiarid watershed and will likely become more frequent and intense in the future under the effects of climate change.

54 ENVIRONMENTAL SCIENCES↗

The effect of wind and currents on gas exchange in an estuarine system

The objectives were to develop a non-volatile tracer to use in gas exchange experiments in laterally unconfined systems and to study applications of deliberate tracers in limnology and oceanography. Progress was made on both fronts but work on the development of the non-volatile tracer proved to be more difficult and labor intensive that anticipated so no field experiments using non-volatile tracers was performed as yet. In the search for a suitable non-volatile tracer for an ocean scale gas exchange experiment a tracer was discovered which does not have the required sensitivity for a large scale experiment, but is very easy to analyze and will be well suited for smaller experiments such as gas exchange determinations on rivers and streams. Sulfur hexafluoride, SF6, was used successfully as a volatile tracer along with tritium as a non-volatile tracer to study gas exchange rates from a primary stream. This is the first gas exchange experiment in which gas exchange rates were determined on a head water stream where significant groundwater input occurs along the reach. In conjunction with SF6, Radon-222 measurements were performed on the groundwater and in the stream. The feasibility of using a combination of SF6 and radon is being studied to determine groundwater inputs and gas exchange of rates in streams with significant groundwater input without using a non-volatile tracer.

Broecker, W. S.↗