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Optimal preparation of the ECC ozonesonde

The ECC background current was identified as the removal of residual tri-iodide (iodine) as the cell approaches equilibrium. The altitude dependence of this source of the background current is expected to be only slowly changed in the troposphere with a more rapid decrease in the stratosphere. Oxygen does not play a role in the background current except in the unlikely situation where the electrodes have had all forms of iodine removed from them and the electrodes have not re-equilibrated with the sonde solutions before use. A solution mass transport parameter in the ECC was identified and its altitude dependence determined. The mass transport of tri-iodide dominates in the chemical transduction of ozone to electrical signal. The effect of the mass transport on the ECC background current is predicted. An electrochemical model of the ECC has been developed to predict the response of the ECC to various ozone vertical profiles. The model corresponds very closely to the performance of the ECC in the laboratory. Based on this model, an ECC with no background current is predicted to give total ozone values within 1% of the correct value, although the vertical profile may be in error by as much as + or - 15%.

Thornton, D. C.↗

Theoretical studies of solar lasers and converters

The previously constructed one dimensional model for the simulated operation of an iodine laser assumed that the perfluoroalkyl iodide gas n-C3F7I was incompressible. The present study removes this simplifying assumption and considers n-C3F7I as a compressible fluid.

Heinbockel, John H.↗

Characterization of hot hydrogen-atom reactions by kinetic spectrography.

The flash photolysis of hydrogen iodide in the presence of nitrous oxide, carbon dioxide, and water has been investigated by kinetic spectroscopy. Although the fraction of hydrogen iodide dissociated was very large, the only observable intermediate was imidogen. It was demonstrated that the rapid removal of imidogen and the apparent absence of hydroxyl radicals in each case is a result of the following two reactions, respectively: (1) NH + HI yields NH2 + I; and (2) OH + HI yields H2O + I.

Tomalesky, R. E.↗

A New Method to Correct the Electrochemical Concentration Cell (ECC) Ozonesonde Time Response and its Implications for "Background Current" and Pump Efficiency

The electrochemical concentration cell (ECC) ozonesonde has been the main instrument for in situ profiling of ozone worldwide; yet, some details of its operation, which contribute to the ozone uncertainty budget, are not well understood. Here, we investigate the time response of the chemical reactions inside the ECC and how corrections can be used to remove some systematic biases. The analysis is based on the understanding that two reaction pathways involving ozone occur inside the ECC that generate electrical currents on two very different timescales. The main fast-reaction pathway with a time constant of about 20 s is due the conversion of iodide to molecular iodine and the generation of two free electrons per ozone molecule. A secondary slow-reaction pathway involving the buffer generates an excess current of about 2 %–10 % with a time constant of about 25 min. This excess current can be interpreted as what has conventionally been considered the “background current”. This contribution can be calculated and removed from the measured current instead of the background current. Here we provide an algorithm to calculate and remove the contribution of the slow-reaction pathway and to correct for the time lag of the fast-reaction pathway. This processing algorithm has been applied to ozonesonde profiles at Costa Rica and during the Central Equatorial Pacific Experiment (CEPEX) as well as to laboratory experiments evaluating the performance of ECC ozonesondes. At Costa Rica, where a 1 % KI, 1/10th buffer solution is used, there is no change in the derived total ozone column; however, in the upper troposphere and lower stratosphere, average reported ozone concentrations increase by up to 7 % and above 30 km decrease by up to 7 %. During CEPEX, where a 1 % KI, full-buffer solution was used, ozone concentrations are increased mostly in the upper troposphere, with no change near the top of the profile. In the laboratory measurements, the processing algorithms have been applied to measurements using the majority of current sensing solutions and using only the stronger pump efficiency correction reported by Johnson et al. (2002). This improves the accuracy of the ECC sonde ozone profiles, especially for low ozone concentrations or large ozone gradients and removes systematic biases relative to the reference instruments. In the surface layer, operational procedures prior to launch, in particular the use of filters, influence how typical gradients above the surface are detected. The correction algorithm may report gradients that are steeper than originally reported, but their uncertainty is strongly influenced by the prelaunch procedures.

electrochemical concentration cell (ECC) ozonesond↗

Iodine - Its possible role in tropospheric photochemistry

A detailed study of the photochemistry of iodine and its oxides indicates that iodine species may play an important role in the tropospheric photochemical system. Methyl iodide, often observed in the marine troposphere with an average concentration of 5-10 ppt, is photolyzed and thereby produces I atoms. Chemical interactions with O3, HxOy, and NOx cause I to be converted to other inorganic compounds such as IO, HOI, IONO2, and I2. The production of these species and their subsequent recycling back to I can lead to the catalytic removal of tropospheric O3, the enhancement of the NO2/NO ratio, the destruction of HxOy free radicals, and the conversion of HO2 to OH. Ultimately, tropospheric inorganic iodine is removed by heterogeneous processes. Calculations using a numerical model to simulate tropospheric photochemistry indicate that iodine may have a strong impact upon the atmospheric O3-NOx-HxOy system. The magnitude of these effects is dependent upon the value of several uncertain rate constants and the primary source distributions of CH3I and other organic and inorganic iodine compounds.

Chameides, W. L.↗

Materials International Space Station Experiment (MISSE): Overview, Accomplishments and Future Needs

Materials and devices used on the exterior of spacecraft in low Earth orbit (LEO) are subjected to environmental threats that can cause degradation in material properties, possibly threatening spacecraft mission success. These threats include: atomic oxygen (AO), ultraviolet and x-ray radiation, charged particle radiation, temperature extremes and thermal cycling, micrometeoroid and debris impacts, and contamination. Space environmental threats vary greatly based on spacecraft materials, thicknesses and stress levels, and the mission environment and duration. For more than a decade the Materials International Space Station Experiment (MISSE) has enabled the study of the long duration environmental durability of spacecraft materials in the LEO environment. The overall objective of MISSE is to test the stability and durability of materials and devices in the space environment in order to gain valuable knowledge on the performance of materials in space, as well as to enable lifetime predictions of new materials that may be used in future space flight. MISSE is a series of materials flight experiments, which are attached to the exterior of the International Space Station (ISS). Individual experiments were loaded onto suitcase-like trays, called Passive Experiment Containers (PECs). The PECs were transported to the ISS in the Space Shuttle cargo bay and attached to, and removed from, the ISS during extravehicular activities (EVAs). The PECs were retrieved after one or more years of space exposure and returned to Earth enabling post-flight experiment evaluation. MISSE is a multi-organization project with participants from the National Aeronautics and Space Administration (NASA), the Department of Defense (DoD), industry and academia. MISSE has provided a platform for environmental durability studies for thousands of samples and numerous devices, and it has produced many tangible impacts. Ten PECs (and one smaller tray) have been flown, representing MISSE 1 through MISSE 8, yielding long-duration space environmental performance and durability data that enable material validation, processing recertification and space qualification; improved predictions of materials and component lifetimes in space; model verification and development; and correlation factors between space-exposure and ground-facilities enabling more accurate in-space performance predictions based on ground-laboratory testing. A few of the many experiment results and observations, and their impacts, are provided. Those highlighted include examples on improved understanding of atomic oxygen scattering mechanisms, LEO coating durability results, and polymer erosion yields and their impacts on spacecraft design. The MISSE 2 Atomic Oxygen Scattering Chamber Experiment discovered that the peak flux of scattered AO was determined to be 45 deg from normal incidence, not the model predicted cosine dependence. In addition, the erosion yield (E(sub y)) of Kapton H for AO scattered off oxidized-Al is 22% of the E(sub y) of direct AO impingement. These results were used to help determine the degradation mechanism of a cesium iodide detector within the Hubble Space Telescope Cosmic Origins Spectrograph Experiment. The MISSE 6 Indium Tin Oxide (ITO) Degradation Experiment measured surface electrical resistance of ram and wake ITO coated samples. The data confirmed that ITO is a stable AO protective coating, and the results validated the durability of ITO conductive coatings for solar arrays for the Atmosphere-Space Transition 2 Explorer program. The MISSE 2, 6 and 7 Polymer Experiments have provided LEO AO Ey data on over 120 polymer and composites samples. The flight E(sub y) values were found to range from 3.05 x 10(exp -26) cu cm/atom for the AO resistant polymer CORIN to 9.14 x 10(exp -26) cu cm/atom for polyoxymethylene (POM). In addition, flying the same polymers on different missions has advanced the understanding of the AO E(sub y) dependency on solar exposure for polymers containing fluorine. The MISSE polymer results are highly requested and have impacted spacecraft design for WorldView-2 & -3, the Global Precipitation Measurement-Microwave Imager, and other spacecraft. The flight data has enabled the development of an Atomic Oxygen Erosion Predictive Tool that allows the erosion prediction of new and non-flown polymers. The data has also been used to develop a new NASA Technical Standards Handbook "Spacecraft Polymers Atomic Oxygen Durability Handbook." Many intangible benefits have also been derived from MISSE. For example, over 40 students have collaborated on Glenn's MISSE experiments, which have resulted in greater than $80K in student scholarships and awards in national and international science fairs. Students have also given presentations and won poster competition awards at international space conferences.

Flight Experiment↗