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Chapter 4 - Ozonesondes: Instrumentation and Data Applications

The ozonesonde instrument, launched on a standard weather balloon along with a radiosonde, has been used for more than 50 years to measure ozone concentrations in the troposphere to mid-stratosphere. The measurement is based on an electrochemical reaction, avoiding associated with optical techniques, and can achieve a 5% or better accuracy and precision when careful preparation and data-processing methods are employed. Instrument details are described and the global ozonesonde network illustrated. The use of the ozonesonde in the complement of ground-based instruments that validate satellite ozone instruments is described. Satellite data in turn help maintain consistency of long-term ozonesonde measurements.

tropospheric ozone↗

Influence of several metal ions on the gelation activation energy of silicon tetraethoxide

The effects of nine metal cations (Li(+), Na(+), Mg(2+), Ca(2+), Sr(2+), Cu(2+), Al(3+), La(3+), and Y(3+) on silica gel formation has been investigated by studying the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) in the presence of metal nitrates. The influence of water: TEOS mole ratio, metal ion concentration, and the reaction temperature has been investigated. The overall activation energy for gel formation has been determined from the temperature dependence of the time of gelation for each system. The activation energy for -Si-O-Si- network formation is found to be 54.5 kJ/mol. The gel formation time as well as the activation energy sharply increase in the presence of Cu(2+), Al(3+), La(3+) and Y(3+). In contrast, the presence of Li(+), Na(+), Mg(2+), Ca(2+), or, Sr(2+) lowers the gelation time, but has no appreciable effect on the activation energy. This difference may be attributed to the participation or nonparticipation of the metal ions in the formation of the three-dimensional polymeric network during the polycondensation step. The concentration of metal ion (Mg(2+), Ca(2+), Y(3+) or the water: TEOS mole ratio had no appreciable effect on the gelation activation energy. A simple test has been proposed to determine whether a metal ion would act as a network intermediate or modifier in silica and other glassy networks.

Bansal, Narottam P.↗

Influence of several metal ions on the gelation activation energy of silicon tetraethoxide

The effects of nine metal cations Li(+), Na(+), Mg(2+), Ca(2+), Sr(2+), Cu(2+), Al(3+), La(3+), and Y(3+) on silica gel formation has been investigated by studying the hydrolysis and polycondensation of silicon tetraethoxide (TEOS) in the presence of metal nitrates. The influence of water:TEOS mole ratio, metal ion concentration, and the reaction temperature has been investigated. The overall activation energy for gel formation has been determined from the temperature dependence of the time of gelation for each system. The activation energy for -Si-O-Si- network formation is found to be 54.5 kJ/mol. The gel formation time as well as the activation energy sharply increase in the presence of Cu(2+), Al(3+), La(3+) and Y(3+). In contrast, the presence of Li(+), Na(+), Mg(2+), Ca(2+), or Sr(2+) lowers the gelation time, but has no appreciable effect on the activation energy. This difference may be attributed to the participation or nonparticipation of the metal ions in the formation of the three-dimensional polymeric network during the polycondensation step. The concentration of metal ion Mg(2+), Ca(2+), Y(3+) or the water:TEOS mole ratio had no appreaciable effect on the gelation activation energy. A simple test has been proposed to determine whether a metal ion would act as a network intermediate or modifier in silica and other glassy networks.

Bansal, Narottam P.↗

Autonomous Coordination of Science Observations Using Multiple Spacecraft

This software provides capabilities for autonomous cross-cueing and coordinated observations between multiple orbital and landed assets. Previous work has been done in re-tasking a single Earth orbiter or a Mars rover in response to that craft detecting a science event. This work enables multiple spacecraft to communicate (over a network designed for deep-space communications) and autonomously coordinate the characterization of such a science event. This work investigates a new paradigm of space science campaigns where opportunistic science observations are autonomously coordinated among multiple spacecraft. In this paradigm, opportunistic science detections can be cued by multiple assets where a second asset is requested to take additional observations characterizing the identified surface feature or event. To support this new paradigm, an autonomous science system for multiple spacecraft assets was integrated with the Interplanetary Network DTN (Delay Tolerant Network) to provide communication between spacecraft assets. This technology enables new mission concepts that are not feasible with current technology. The ability to rapidly coordinate activities across spacecraft without requiring ground in the loop enables rapid reaction to dynamic events across platforms, such as a survey instrument followed by a targeted high resolution instrument, as well as regular simultaneous observations.

Estlin, Tara A.↗

Evaluating Long-Term Changes in Atmospheric Ozone

Ozonesondes have made inexpensive, accurate measurements of ozone from the ground to 30km for more than 50 years. The data are used extensively for trend analyses and for evaluation of satellite and model data products, and are also part of climatologies that are used as a priori data for satellite retrievals. They are essential as a transfer standard when merging shorter satellite-derived time series, and are the most important source of trend-quality long-term records below about 18 km. The importance of long-term ozonesonde records as a stable reference has led to increased attention to quantifying uncertainties and changes in ozonesonde data. Based on past intercomparison data, ECC sondes show a modest (~1-5%) high bias with respect to UV-absorption measurements (including MOZAIC-IAGOS) in the troposphere, with an uncertainty of 5%, but no evidence of a change with time. Other sonde types show an increase of 5-20% in sensitivity to tropospheric ozone from 1970-1995. Agreement in the stratosphere is much better. In the past 20 years ozonesonde precision has improved by a factor of 2, primarily through the adoption of strict standard operating procedures. In addition, many of the most important ozonesonde records have been re-evaluated and corrected, and detailed estimates made of their biases and uncertainties. Corrections to historical data for known issues may reduce biases but simultaneously introduce additional uncertainties. The uncertainty budget for the ozone partial pressure reading has contributions from stoichiometry, cell background current, pump efficiency and temperature, sensing solution type and volume. The much-discussed “background current” has recently been shown to be primarily related to reaction stoichiometry. Several quality assurance issues remain, but are tractable problems that can be addressed with further research. This will be required if the present goal of better than 5% overall uncertainty throughout the global ozonesonde network is to be achieved. Finally, the importance of regular sonde intercomparisons, employing UV photometers traceable to the modern UV-absorption standard, and of regular comparison of operational station records with multiple satellite sensors, is emphasized.

Ozonesondes↗

Kinetics of hexacelsian to celsian phase transformation in SrAl2Si2O8

The kinetics of hexacelsian to celsian phase transformation in SrAl2Si2O8 have been investigated. Phase pure hexacelsian was prepared by heat treatment of glass flakes at 990 C for 10 h. Bulk hexacelsian was isothermally heat treated at 1026, 1050, 1100, 1152, and 1200 C for various times. The amounts of monoclinic celsian formed were determined using quantitative X-ray diffraction. Values of reaction rate constant, k, at various temperatures were evaluated from the Avrami equation. The Avrami parameter was determined to be 1.1, suggesting a diffusionless, one-dimensional transformation mechanism. From the temperature dependence of k, the activation energy for this reaction was evaluated to be 527 plus or minus 50 kJ/mole (126 plus or minus 12 kcal/mole). This value is consistent with a mechanism involving the transformation of the layered hexacelsian structure to a three-dimensional network celsian structure which necessitates breaking of the strongest bonds, the Si-O bonds.

Bansal, Narottam P.↗

Kinetics of hexacelsian-to-celsian phase transformation in SrAl2Si2O8

The kinetics of hexacelsian to celsian phase transformation in SrAl2Si2O8 have been investigated. Phase pure hexacelsian was prepared by heat treatment of glass flakes at 990 C for 10 h. Bulk hexacelsian was isothermally heat treated at 1026, 1050, 1100, 1152, and 1200 C for various times. The amounts of monoclinic celsian formed were determined using quantitative X-ray diffraction. Values of reaction rate constant, k, at various temperatures were evaluated from the Avrami equation. The Avrami parameter was determined to be 1.1, suggesting a diffusionless, one-dimensional transformation mechanism. From the temperature dependence of k, the activation energy for this reaction was evaluated to be 527 plus or minus 50 kJ/mole (126 plus or minus 12 kcal/mole). This value is consistent with a mechanism involving the transformation of the layered hexacelsian structure to a three-dimensional network celsian structure which necessitates breaking of the strongest bonds, the Si-O bonds.

Bansal, Narottam P.↗

Using neural networks and Dyna algorithm for integrated planning, reacting and learning in systems

The traditional AI answer to the decision making problem for a robot is planning. However, planning is usually CPU-time consuming, depending on the availability and accuracy of a world model. The Dyna system generally described in earlier work, uses trial and error to learn a world model which is simultaneously used to plan reactions resulting in optimal action sequences. It is an attempt to integrate planning, reactive, and learning systems. The architecture of Dyna is presented. The different blocks are described. There are three main components of the system. The first is the world model used by the robot for internal world representation. The input of the world model is the current state and the action taken in the current state. The output is the corresponding reward and resulting state. The second module in the system is the policy. The policy observes the current state and outputs the action to be executed by the robot. At the beginning of program execution, the policy is stochastic and through learning progressively becomes deterministic. The policy decides upon an action according to the output of an evaluation function, which is the third module of the system. The evaluation function takes the following as input: the current state of the system, the action taken in that state, the resulting state, and a reward generated by the world which is proportional to the current distance from the goal state. Originally, the work proposed was as follows: (1) to implement a simple 2-D world where a 'robot' is navigating around obstacles, to learn the path to a goal, by using lookup tables; (2) to substitute the world model and Q estimate function Q by neural networks; and (3) to apply the algorithm to a more complex world where the use of a neural network would be fully justified. In this paper, the system design and achieved results will be described. First we implement the world model with a neural network and leave Q implemented as a look up table. Next, we use a lookup table for the world model and implement the Q function with a neural net. Time limitations prevented the combination of these two approaches. The final section discusses the results and gives clues for future work.

Lima, Pedro↗

Structural Model for the Flip-Flop Action in Thiamin Pyrophosphate-Dependent Human Pyruvate Dehydrogenase

The derivative of vitamin B1 thiamin pyrophosphate (TPP) is a cofactor of enzymes performing catalysis in pathways of energy production, including (i) decarboxylation of alpha-keto acids followed by (ii) transketolation. These enzymes have shown a common mechanism of TPP activation by imposing an active V-conformation of this coenzyme that brings the N4 atom of the aminopyrimidine ring to the distance required for the intramolecular C-H N hydrogen-bonding with the C2- atom of the thiazolium ring. The reactive C2 atom of TPP is the nucleophile that attacks the carbonyl carbon of different substrates used by the TPP-dependent enzymes. The structure of the heterotetrameric human pyruvate dehydrogenase (Elp) recently determined in our laboratory (1) revealed the association pattern of the subunits and the specifics of two chemically equivalent cofactor binding sites. Dynamic nonequivalence of these two cofactor sites directs the flip-flop action of this enzyme, depending upon which two active sites effect each other (2). The crystal structure derived from the holo-form of Elp provided the basis for the model of the flip-flop action of Elp in which different steps of the catalytic reaction are performed in each of the two cofactor sites at any given moment, where these steps are governed by the concerted shuttle-like motion of the subunits. It is further proposed that balancing a hydrogen-bond network and related cofactor geometry determine the continuity of catalytic events.

Ciszak, Ewa↗

Life and death in the microcirculation: a role for angiotensin II

OBJECTIVE: Angiotensin II (ANGII) plays a critical role in the maintenance of the microcirculation and in the anatomical loss of microvessels (rarefaction) that occurs in low renin forms of hypertension and in animals fed a high-salt diet. Elevations in sodium intake can trigger a series of hemodynamic and hormonal responses culminating in a substantial rarefaction of small arterioles and capillaries in both normal and reduced renal mass hypertensive rats. METHODS: Immunohistochemistry, Northern blot, and reverse transcription-polymerase chain reaction (RT-PCR) analysis of microdissected blood vessels were used to localize ANGII receptors in the microcirculation. Chronic infusion of ANGII and other physiologic and pharmacologic manipulations of the reninangiotensin system in rats was combined with morphologic and mathematical analysis of the network architecture. RESULTS: We have shown that rarefaction of the microcirculation can cause an increase in total peripheral resistance, reduced tissue perfusion, decreased oxygen delivery, and impaired organ function. Although the mechanisms by which this occurs are not well understood, a number of key observations point to a role for the renin-angiotensin system in this effect. First, ANGII infused systemically at subpressor levels, or locally into the skeletal muscle interstitium, can induce significant microvessel growth. Second, localization of ANGII receptor proteins by immunohistochemistry and Western blotting and RNA localization by RT-PCR confirm the presence of AT1 receptors, which are growth-stimulatory, and AT2 receptors, which are growth-inhibitory in the microcirculation. Third, maintenance of ANGII at normal levels during periods of hypertension or high-salt diet completely eliminates rarefaction. CONCLUSIONS: Taken together, these results support the hypothesis that ANGII acting through AT1- and AT2-receptor mechanisms modulate vessel density during high-salt diet and hypertension.

Review↗

Machine Learning Applications to Metal-Silicate Equilibria and their Insights into Core Formation

An extensive number of studies have experimentally investigated how elements distribute between metal and silicate phases, to better constrain core-mantle chemical equilibrium. Here, we present a new database compiling all (to our knowledge) experimental data on liquid metal-silicate partitioning from 118 peer-reviewed publications. We applied various machine learning techniques to gain further insights into these partitioning equilibria and their dependencies. We performed a network analysis to investigate the relationship between experiments and partition coefficients, which enables visualizing gaps in the experimental dataset and biases related to varying experimental conditions and analytical setup. In addition, semi-empirical thermodynamic models are commonly used to extrapolate these chemical reactions to the wide range of pressure, temperature and compositional conditions of planetary differentiation. These models are based on linear regressions that assume continuous relationship between partition coefficients and experimental variables. Here, we considered random forest regressions, which are algorithms based on ensembles of decision trees and does not consider continuous effects of each variable. The application of this regression significantly improves the prediction of metal-silicate partitioning for several elements including Ni, Si and Cr. We will show how this new approach improves our understanding of elemental exchange between metal and silicate and their implications for the Earth’s core formation.

siderophile element↗

Deriving Global OH Abundance and Atmospheric Lifetimes for Long-Lived Gases: A Search for CH3CCl3 Alternatives

An accurate estimate of global hydroxyl radical (OH) abundance is important for projections of air quality, climate, and stratospheric ozone recovery. As the atmospheric mixing ratios of methyl chloroform (CH3CCl3) (MCF), the commonly used OH reference gas, approaches zero, it is important to find alternative approaches to infer atmospheric OH abundance and variability. The lack of global bottom-up emission inventories is the primary obstacle in choosing a MCF alternative. We illustrate that global emissions of long-lived trace gases can be inferred from their observed mixing ratio differences between the Northern Hemisphere (NH) and Southern Hemisphere (SH), given realistic estimates of their NH-SH exchange time, the emission partitioning between the two hemispheres, and the NH versus SH OH abundance ratio. Using the observed long-term trend and emissions derived from the measured hemispheric gradient, the combination of HFC-32 (CH2F2), HFC-134a (CH2FCF3, HFC-152a (CH3CHF2), and HCFC-22 (CHClF2), instead of a single gas, will be useful as a MCF alternative to infer global and hemispheric OH abundance and trace gas lifetimes. The primary assumption on which this multispecies approach relies is that the OH lifetimes can be estimated by scaling the thermal reaction rates of a reference gas at 272 K on global and hemispheric scales. Thus, the derived hemispheric and global OH estimates are forced to reconcile the observed trends and gradient for all four compounds simultaneously. However, currently, observations of these gases from the surface networks do not provide more accurate OH abundance estimate than that from MCF.

Lifetime↗

Coordinating an Autonomous Earth-Observing Sensorweb

A system of software has been developed to coordinate the operation of an autonomous Earth-observing sensorweb. Sensorwebs are collections of sensor units scattered over large regions to gather data on spatial and temporal patterns of physical, chemical, or biological phenomena in those regions. Each sensor unit is a node in a data-gathering/ data-communication network that spans a region of interest. In this case, the region is the entire Earth, and the sensorweb includes multiple terrestrial and spaceborne sensor units. In addition to acquiring data for scientific study, the sensorweb is required to give timely notice of volcanic eruptions, floods, and other hazardous natural events. In keeping with the inherently modular nature of the sensory, communication, and data-processing hardware, the software features a flexible, modular architecture that facilitates expansion of the network, customization of conditions that trigger alarms of hazardous natural events, and customization of responses to alarms. The soft8 NASA Tech Briefs, July 2006 ware facilitates access to multiple sources of data on an event of scientific interest, enables coordinated use of multiple sensors in rapid reaction to detection of an event, and facilitates the tracking of spacecraft operations, including tracking of the acquisition, processing, and downlinking of requested data.

Sherwood, Robert↗

Molnets: An Artificial Chemistry Based on Neural Networks

The fundamental problem in the evolution of matter is to understand how structure-function relationships are formed and increase in complexity from the molecular level all the way to a genetic system. We have created a system where structure-function relationships arise naturally and without the need of ad hoc function assignments to given structures. The idea was inspired by neural networks, where the structure of the net embodies specific computational properties. In this system networks interact with other networks to create connections between the inputs of one net and the outputs of another. The newly created net then recomputes its own synaptic weights, based on anti-hebbian rules. As a result some connections may be cut, and multiple nets can emerge as products of a 'reaction'. The idea is to study emergent reaction behaviors, based on simple rules that constitute a pseudophysics of the system. These simple rules are parameterized to produce behaviors that emulate chemical reactions. We find that these simple rules show a gradual increase in the size and complexity of molecules. We have been building a virtual artificial chemistry laboratory for discovering interesting reactions and for testing further ideas on the evolution of primitive molecules. Some of these ideas include the potential effect of membranes and selective diffusion according to molecular size.

Colombano, Silvano↗

Numerical Modeling of Pressurization of Cryogenic Propellant Tank for Integrated Vehicle Fluid System

This paper presents a numerical model of pressurization of a cryogenic propellant tank for the Integrated Vehicle Fluid (IVF) system using the Generalized Fluid System Simulation Program (GFSSP). The IVF propulsion system, being developed by United Launch Alliance, uses boiloff propellants to drive thrusters for the reaction control system as well as to run internal combustion engines to develop power and drive compressors to pressurize propellant tanks. NASA Marshall Space Flight Center (MSFC) has been running tests to verify the functioning of the IVF system using a flight tank. GFSSP, a finite volume based flow network analysis software developed at MSFC, has been used to develop an integrated model of the tank and the pressurization system. This paper presents an iterative algorithm for converging the interface boundary conditions between different component models of a large system model. The model results have been compared with test data.

Majumdar, Alok K.↗

Numerical Modeling of an Integrated Vehicle Fluids System Loop for Pressurizing a Cryogenic Tank

This paper presents a numerical model of the pressurization loop of the Integrated Vehicle Fluids (IVF) system using the Generalized Fluid System Simulation Program (GFSSP). The IVF propulsion system, being developed by United Launch Alliance to reduce system weight and enhance reliability, uses boiloff propellants to drive thrusters for the reaction control system as well as to run internal combustion engines to develop power and drive compressors to pressurize propellant tanks. NASA Marshall Space Flight Center (MSFC) conducted tests to verify the functioning of the IVF system using a flight-like tank. GFSSP, a finite volume based flow network analysis software developed at MSFC, has been used to support the test program. This paper presents the simulation of three different test series, comparison of numerical prediction and test data and a novel method of presenting data in a dimensionless form. The paper also presents a methodology of implementing a compressor map in a system level code.

LeClair, A. C.↗

Tough, processable simultaneous semi-interpenetrating polyimides

A high temperature semi-interpenetrating polymer network (semi-IPN) was developed which had significantly improved processability, damage tolerance, and mechanical performance when compared to the commercial Thermid materials. This simultaneous semi-IPN was prepared by mixing a thermosetting polyimide with a thermoplastic monomer precursor solution (NR150B2) and allowing them to react upon heating. This reaction occurs at a rate which decreases the flow and broadens the processing window. Upon heating at a higher temperature, there is an increase in flow. Because of the improved flow properties, broadened processing window and enhanced toughness, high strength polymer matrix composites, adhesives and molded articles can now be prepared from the acetylene endcapped polyimides which were previously inherently brittle and difficult to process.

Pater, Ruth H.↗

Microgravity Drill and Anchor System

This work is a method to drill into a rock surface regardless of the gravitational field or orientation. The required weight-on-bit (WOB) is supplied by a self-contained anchoring mechanism. The system includes a rotary percussive coring drill, forming a complete sampling instrument usable by robot or human. This method of in situ sample acquisition using micro - spine anchoring technology enables several NASA mission concepts not currently possible with existing technology, including sampling from consolidated rock on asteroids, providing a bolt network for astronauts visiting a near-Earth asteroid, and sampling from the ceilings or vertical walls of lava tubes and cliff faces on Mars. One of the most fundamental parameters of drilling is the WOB; essentially, the load applied to the bit that allows it to cut, creating a reaction force normal to the surface. In every drilling application, there is a minimum WOB that must be maintained for the system to function properly. In microgravity (asteroids and comets), even a small WOB could not be supported conventionally by the weight of the robot or astronaut. An anchoring mechanism would be needed to resist the reactions, or the robot or astronaut would push themselves off the surface and into space. The ability of the system to anchor itself to a surface creates potential applications that reach beyond use in low gravity. The use of these anchoring mechanisms as end effectors on climbing robots has the potential of vastly expanding the scope of what is considered accessible terrain. Further, because the drill is supported by its own anchor rather than by a robotic arm, the workspace is not constrained by the reach of such an arm. Yet, if the drill is on a robotic arm, it has the benefit of not reflecting the forces of drilling back to the arm s joints. Combining the drill with the anchoring feet will create a highly mobile, highly stable, and highly reliable system. The drilling system s anchor uses hundreds of microspine toes that independently find holes and ledges on a rock to create an anchor. Once the system is anchored, a linear translation mechanism moves the drill axially into the surface while maintaining the proper WOB. The linear translation mechanism is composed of a ball screw and stepper motor that can translate a carriage with high precision and applied load. The carriage slides along rails using self-aligning linear bearings that correct any axial misalignment caused by bending and torsion. The carriage then compresses a series of springs that simultaneously transmit the load to the drill along the bit axis and act as a suspension that compensates for the vibration caused by percussive drilling. The drill is a compacted, modified version of an off-the-shelf rotary percussive drill, which uses a custom carbide-tipped coring bit. By using rotary percussive drilling, the drill time is greatly reduced. The percussive action fractures the rock debris, which is removed during rotation. The final result is a 0.75-in. (.1.9- cm) diameter hole and a preserved 0.5- in. (.1.3-cm) diameter rock core. This work extends microspine technology, making it applicable to astronaut missions to asteroids and a host of robotic sampling concepts. At the time of this reporting, it is the first instrument to be demonstrated using microspine anchors, and is the first self-contained drill/anchor system to be demonstrated that is capable of drilling in inverted configurations and would be capable of drilling in microgravity.

Parness, Aaron↗