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Gas-phase microactuation using kinetically controlled surface states of ultrathin catalytic sheets

Biological systems convert chemical energy into mechanical work by using protein catalysts that assume kinetically controlled conformational states. Synthetic chemomechanical systems using chemical catalysis have been reported, but they are slow, require high temperatures to operate, or indirectly perform work by harnessing reaction products in liquids (e.g., heat or protons). Here, we introduce a bioinspired chemical strategy for gas-phase chemomechanical transduction that sequences the elementary steps of catalytic reactions on ultrathin (<10 nm) platinum sheets to generate surface stresses that directly drive microactuation (bending radii of 700 nm) at ambient conditions (T = 20 °C; P total = 1 atm). When fueled by hydrogen gas and either oxygen or ozone gas, we show how kinetically controlled surface states of the catalyst can be exploited to achieve fast actuation (600 ms/cycle) at 20 °C. Finally, we also show that the approach can integrate photochemically controlled reactions and can be used to drive the reconfiguration of microhinges and complex origami- and kirigami-based microstructures.

42 ENGINEERING↗

Pulling Results Out of Thin Air: Four Years of Ozone and Greenhouse Gas Measurements by the Alpha Jet Atmospheric Experiment (AJAX)

The Alpha Jet Atmospheric eXperiment (AJAX) has been measuring atmospheric ozone, carbon dioxide, methane and meteorological parameters from near the surface to 8000 m since January 2011. The main goals are to study photochemical ozone production and the impacts of extreme events on western US air quality, provide data to support satellite observations and aid in the quantification of emission sources e.g. wildfires, urban outflow, diary and oil and gas. The aircraft is based at Moffett Field and flies multiple times a month to sample vertical profiles at selected sites in California and Nevada, providing long-term data records at these sites. AJAX is also uniquely positioned to launch with short notice sampling flights in rapid response to extreme events e.g. the 2013 Yosemite Rim fire. This talk will focus on the impacts of vertical transport on surface air quality, and investigation of emission sources from diaries and wildfires.

AJAX↗

Remote sensing of the ozone profile in the lower stratosphere using UV and IR measurements from Nimbus 4

With a three-parameter analytical model, the ozone profile below 10 mbar to the surface is derived from the Nimbus 4 satellite backscattered ultraviolet and infrared measurements. Comparison of the derived profiles with those observed by ozonesondes shows that gross features are satisfactorily reproduced. Meridional cross section of the ozone partial pressure derived from the satellite data reveal the significant equator-to-pole features, as well as seasonal variability. An examination of the sensitivity of the method shows that an error in infrared radiance of approximately 1 erg leads to an error of about 10 mbar in the weighted mean pressure of the ozone layer in the tropics.

Prabhakara, C.↗

Trends in the Vertical Distribution of Ozone: A Comparison of Two Analyses of Ozonesonde Data

We present the results of two independent analyses of ozonesonde measurements of the vertical profile of ozone. For most of the ozonesonde stations we use data that were recently reprocessed and reevaluated to improve their quality and internal consistency. The two analyses give similar results for trends in ozone. We attribute differences in results primarily to differences in data selection criteria and in utilization of data correction factors, rather than in statistical trend models. We find significant decreases in stratospheric ozone at all stations in middle and high latitudes of the northern hemisphere from 1970 to 1996, with the largest decreases located between 12 and 21 km, and trends of -3 to -10 %/decade near 17 km. The decreases are largest at the Canadian and the most northerly Japanese station, and are smallest at the European stations, and at Wallops Island, U.S.A. The mean mid-latitude trend is largest, -7 %/decade, from 12 to 17.5 km for 1970-96. For 1980-96, the decrease is more negative by 1-2 %/decade, with a maximum trend of -9 %/decade in the lowermost stratosphere. The trends vary seasonally from about 12 to 17.5 km, with largest ozone decreases in winter and spring. Trends in tropospheric ozone are highly variable and depend on region. There are decreases or zero trends at the Canadian stations for 1970-96, and decreases of -2 to -8 %/decade for the mid-troposphere for 1980-96; the three European stations show increases for 1970-96, but trends are close to zero for two stations for 1980-96 and positive for one; there are increases in ozone for the three Japanese stations for 1970-96, but trends are either positive or zero for 1980-96; the U.S. stations show zero or slightly negative trends in tropospheric ozone after 1980. It is not possible to define reliably a mean tropospheric ozone trend for northern mid-latitudes, given the small number of stations and the large variability in trends. The integrated column trends derived from the sonde data are consistent with trends derived from both surface based and satellite measurements of the ozone column.

Loogan, J. A.↗

Two-dimensional simulation of Pinatubo aerosol and its effect on stratospheric ozone

This paper presents time-dependent simulations of the response of the stratosphere to the injection into the atmosphere of massive amounts of sulfur during the eruption of Mt. Pinatubo (The Philippines) in June 1991. The study is based on a coupled two-dimensional chemical-dynamical-radiative model to which a microphysical model for sulfate aerosol formation and fate has been added. The study suggests that, during the first year (July 1991 to June 1992) following the volcanic eruption, the observed changes in the ozone amount integrated between 65 deg S and 65 deg N were caused primarily by changes in the meridional circulation (associated with heating by the volcanic cloud in the tropics) and in the photolysis rate of molecules such as ozone (associated with backscattering of light by the cloud). During the second year after the eruption, as the aerosol was dispersed at all latitudes and, in particular, reached the polar region, the largest contribution to ozone reduction resulted from the heterogeneous chemical conversion of N2O5 and ClONO2 on the surface of the aerosol particles. The conversion of the latter compound, and hence the magnitude of the calculated ozone depletion, is highly dependent on the temperature in the lower stratosphere. Despite the fact that the surface area provided by aerosol particles decreased during the second year following the eruption, the calculated ozone depletion remained significant because the conversion of N2O5 is insensitive to the aerosol surface area density for values larger than 1-10 sq microns/cu cm (depending on latitude). The predicted reduction in ozone at 20 km in March during the third year (July 1993 to June 1994) of the model integration is smaller by a factor of 2 than it was during the second year.

Tie, Xuexi↗

Calculation of the relative influence of cloud layers on received ultraviolet and integrated solar radiation

Discrete ordinate radiative transfer calculations are used to examine the relative influence of cloud layers on the received ultraviolet flux and the received solar energy for a plane parallel atmosphere. The wavelength dependence for the cloud influence on the integrated solar radiation is primarily a function of the interaction of the cloud layer with the surrounding atmosphere and the underlying surface. It is found that for uv wavelengths greater than 300 nm, the ratio of uv to solar energy flux transmission through the atmosphere is insensitive to changes of cloud height, cloud scattering parameters and surface albedo (for realistic values), but is dependent on cloud thickness. For wavelengths approaching and less than 300 nm, absorption by tropospheric ozone results in sensitivity to cloud height and surface albedo.

Spinhirne, J. D.↗

Surface erythemal UV irradiance in the continental United States derived from ground-based and OMI observations: quality assessment, trend analysis and sampling issues

Surface full-sky erythemal dose rate (EDR) from the Ozone Monitoring Instrument (OMI) at both satellite overpass time and local noon time is evaluated against ground measurements at 31 sites from the US Department of Agriculture's (USDA) UV-B Monitoring and Research Program (UVMRP) over the period of 2005–2017. We find that both OMI overpass and solar noon time EDR are highly correlated with the measured counterparts (with a linear correlation coefficient of 0.90 and 0.88, respectively). Although the comparison statistics are improved with a longer time window (0.5–1.0 h) for pairing surface and OMI measurements, both OMI overpass and local noon time EDRs have 7 % overestimation that is larger than 6 % uncertainty in the ground measurements and show different levels of dependence on solar zenith angle (SZA) and to lesser extent on cloud optical depth. The ratio of EDR between local noon and OMI overpass time is often (95 % in frequency) larger than 1 with a mean of 1.18 in the OMI product; in contrast, the same ratio from surface observation is normally distributed with 22 % of the times less than 1 and a mean of 1.38. This contrast in part reflects the deficiency in the OMI surface UV algorithm that assumes constant atmospheric conditions between overpass and noon time. The probability density functions (PDFs) for both OMI and ground measurements of noontime EDR are in statistically significant agreement, showing dual peaks at ∼20 and ∼200 mW/sq. m, respectively; the latter is lower than 220 mW/ sq. m, the value at which the PDF of daily EDR from ground measurements peaks, and this difference indicates that the largest EDR value for a given day may not often occur at local noon. Lastly, statistically significant positive trends of EDR are found in the northeastern US in OMI data, but opposite trends are found within ground-based data (regardless of sampling for either noontime or daily averages). While positive trends are consistently found between OMI and surface data for EDR over the southern Great Plains (Texas and Oklahoma), their values are within the uncertainty of ground measurements. Overall, no scientifically sound trends can be found among OMI data for aerosol total and absorbing optical depth, cloud optical depth and total ozone to explain coherently the surface UV trends revealed either by OMI or ground-based estimates; these data also cannot reconcile trend differences between the two estimates (of EDR from OMI and surface observations). Future geostationary satellites with better spatiotemporal resolution data should help overcome spatiotemporal sampling issues inherent in OMI data products and therefore improve the estimates of surface UV flux and EDR from space.

Ozone Monitoring Instrument (OMI)↗

Convective Distribution of Tropospheric Ozone and Tracers in the Central American ITCZ Region: Evidence from Observations During TC4

During the Tropical Composition, Clouds and Climate Coupling (TC4) experiment that occurred in July and August of 2007, extensive sampling of active convection in the ITCZ region near Central America was performed from multiple aircraft and satellite sensors. As part of a sampling strategy designed to study cloud processes, the NASA ER-2, WB-57 and DC-8 flew in stacked "racetrack patterns" in convective cells. On July 24, 2007, the ER-2 and DC-8 probed an actively developing storm and the DC-8 was hit by lightning. Case studies of this flight, and of convective outflow on August 5, 2007 reveal a significant anti-correlation between ozone and condensed cloud water content. With little variability in the boundary layer and a vertical gradient, low ozone in the upper troposphere indicates convective transport. Because of the large spatial and temporal variability in surface CO and other pollutants in this region, low ozone is a better convective indicator. Lower tropospheric tracers methyl hydrogen peroxide, total organic bromine and calcium substantiate the ozone results. OMI measurements of mean upper tropospheric ozone near convection show lower ozone in convective outflow. A mass balance estimation of the amount of convective turnover below the tropical tropopause transition layer (TTL) is 50%, with an altitude of maximum convective outflow located between 10 and 11 km, 4 km below the cirrus anvil tops. It appears that convective lofting in this region of the ITCZ is either a two-stage or a rapid mixing process, because undiluted boundary layer air is never sampled in the convective outflow.

Avery, Melody↗

Plasma Actuators for Turbomachinery Flow Control

This report is Part I of the final report of NASA Cooperative Agreement contract no. NNX07AC02A. The period of performance was January 1, 2007 to December 31, 2010. This report includes the project summary, a list of publications and reprints of the publications that appeared in archival journals. Part II of the final report includes a Ph.D. dissertation and is published separately as NASA/CR-2012-2172655. The research performed under this project was focused on the operation of surface dielectric barrier discharge (DBD) devices driven by high voltage, nanosecond scale pulses plus constant or time varying bias voltages. The main interest was in momentum production and the range of voltages applied eliminated significant heating effects. The approach was experimental supplemented by computational modeling. All the experiments were conducted at Princeton University. The project provided comprehensive understanding of the associated physical phenomena. Limitations on the performance of the devices for the generation of high velocity surface jets were established and various means for overcoming those limitations were proposed and tested. The major limitations included the maximum velocity limit of the jet due to electrical breakdown in air and across the dielectric, the occurrence of backward breakdown during the short pulse causing reverse thrust, the buildup of surface charge in the dielectric offsetting the forward driving potential of the bias voltage, and the interaction of the surface jet with the surface through viscous losses. It was also noted that the best performance occurred when the nanosecond pulse and the bias voltage were of opposite sign. Solutions include the development of partially conducting surface coatings, the development of a semiconductor diode inlaid surface material to suppress the backward breakdown. Extension to long discharge channels was studied and a new ozone imaging method developed for more quantitative determination of surface jet properties.

Miles, Richard, B↗

Evaluation of NASA's High-Resolution Global Composition Simulations: Understanding a Pollution Event in the Chesapeake Bay During the Summer 2017 OWLETS Campaign

Recirculation of pollutants due to a bay breeze effect is a key meteorological mechanism impacting air quality near urban coastal areas, but regional and global chemical transport models have historically struggled to capture this phenomenon. We present a case study of a high ozone (O3) episode observed over the Chesapeake Bay during the NASA Ozone Water-Land Environmental Transition Study (OWLETS) in summer 2017. OWLETS included a complementary suite of ground-based and airborne observations, with which we characterize the meteorological and chemical context of this event and develop a framework to evaluate model performance. Two publicly-available NASA global high-resolution coupled chemistry-meteorology models (CCMMs) are investigated: GEOS-CF and MERRA2-GMI. The GEOS-CF R squared value for comparisons between the NASA Sherpa C-23 aircraft measurements to the GEOS-CF resulted in good agreement (R squared: 0.67) on July 19th and fair agreement (R squared: 0.55) for July 20th. Compared to surface observations, we find the GEOS-CF product with a 25 x 25 km squared grid box, at an hourly (R squared: 0.62 to 0.87) and 15-minute (R squared: 0.64 to 0.87) interval for six regional sites outperforms the hourly nominally 50 x 50 km squared gridded MERRA2-GMI (R squared: 0.53 to 0.76) for four of the six sites, suggesting it is better capable of simulating complex chemical and meteorological features associated with ozone transport within the Chesapeake Bay airshed. When the GEOS-CF product was compared to the TOLNet LiDAR observations at both NASA Langley Research Center (LaRC) and the Chesapeake Bay Bridge Tunnel (CBBT), the median differences at LaRC were -6 to 8% and at CBBT were ± 7% between 400 to 2000 m ASL. This indicates that, for this case study, the GEOS-CF is able to simulate surface level ozone diurnal cycles and vertical ozone profiles at small scales between the surface level and 2000 m ASL. Evaluating global chemical model simulations at sub-regional scales will help air quality scientists understand the complex processes occurring at small spatial and temporal scales within complex surface terrain changes, simulating nighttime chemistry and deposition, and the potential to use global chemical transport simulations in support of regional and sub-regional field campaigns.

NASA Ozone Water-Land Environmental Transition Stu↗

Observing low-altitude features in ozone concentrations in a shoreline environment via uncrewed aerial systems

Abstract. Ozone is a pollutant formed in the atmosphere by photochemical processes involving nitrogen oxides (NOx) and volatile organic compounds (VOCs) when exposed to sunlight. Tropospheric boundary layer ozone is regularly measured at ground stations and sampled infrequently through balloon, lidar, and crewed aircraft platforms, which have demonstrated characteristic patterns with altitude. Here, to better resolve vertical profiles of ozone within the atmospheric boundary layer, we developed and evaluated an uncrewed aircraft system (UAS) platform for measuring ozone and meteorological parameters of temperature, pressure, and humidity. To evaluate this approach, a UAS was flown with a portable ozone monitor and a meteorological temperature and humidity sensor to compare to tall tower measurements in northern Wisconsin. In June 2020, as a part of the WiscoDISCO20 campaign, a DJI M600 hexacopter UAS was flown with the same sensors to measure Lake Michigan shoreline ozone concentrations. This latter UAS experiment revealed a low-altitude structure in ozone concentrations in a shoreline environment showing the highest ozone at altitudes from 20–100 m a.g.l. These first such measurements of low-altitude ozone via a UAS in the Great Lakes region revealed a very shallow layer of ozone-rich air lying above the surface.

Meteorology & Atmospheric Sciences↗

The atmosphere of Mars

The atmosphere of Mars is essentially a pure carbon dioxide atmosphere that contains a small and seasonably varying amount of water vapor. A number of minor constituents which arise from the interactions of solar radiation with water vapor and carbon dioxide include carbon monoxide, atomic oxygen, molecular oxygen, ozone, and atomic hydrogen. At the surface of Mars the atmospheric pressure is less than one hundredth of the pressure at the surface of the earth. Extensive cloud systems appear on Mars. The structure of the lower Martian atmosphere is discussed together with variations in the lower atmosphere and the characteristics of the upper atmosphere. Reactions of photochemistry are considered along with the atmospheric escape and interactions between the atmosphere and the polar caps.

Barth, C. A.↗

An experimental study of growth and phase change of polar stratospheric cloud particles

This report describes the progress made on understanding phase changes related to solutions which may comprise Polar Stratospheric Clouds. In particular, it is concerned with techniques for investigating specific classes of metastability and phase change which may be important not only in Polar Stratospheric Clouds but in all atmospheric aerosols in general. While the lower level atmospheric aerosol consists of mixtures of (NH4)(SO4)2, NH4HSO4, NaCl among others, there is evidence that aerosol at PSC levels is composed of acid aerosol, either injected from volcanic events (such as Pinatubo) or having diffused upward from the lower atmosphere. In particular, sulfuric acid and nitric acid are known to occur at PSC levels, and are suspected of catalyzing ozone destruction reactions by adsorption on surfaces of crystallized particles. The present study has centered on two approaches: (1) the extent of supercooling (with respect to ice) and supersaturation (with respect to hydrate) and the nature of crystal growth in acid solutions of specific molality; and (2) the nature of growth from the vapor of HNO3 - H2O crystals both on a substrate and on a pre-existing aerosol.

Hallett, John↗

Biological weighting function for the inhibition of phytoplankton photosynthesis by ultraviolet radiation

Severe reduction of stratospheric ozone over Antarctica has focused increasing concern on the biological effects of ultraviolet-B (UVB) radiation (280 to 320 nanometers). Measurements of photosynthesis from an experimental system, in which phytoplankton are exposed to a broad range of irradiance treatments, are fit to an analytical model to provide the spectral biological weighting function that can be used to predict the short-term effects of ozone depletion on aquatic photosynthesis. Results show that UVA (320 to 400 nanometers) significantly inhibits the photosynthesis of a marine diatom and a dinoflagellate, and that the effects of UVB are even more severe. Application of the model suggests that the Antarctic ozone hole might reduce near-surface photosynthesis by 12 to 15 percent, but less so at depth. The experimental system makes possible routine estimation of spectral weightings for natural phytoplankton.

Cullen, John J.↗

Summertime tropospheric ozone distributions over central and eastern Canada

Ozone measurements were obtained between the surface and the 6-km altitude on aircraft flights over central and eastern Canada during the summer 1990 NASA Global Tropospheric Experiment Arctic Boundary Layer Expedition (GTE/ABLE 3B). Tropospheric O3 budgets for these regions were observed to be highly variable and significantly impacted by long-range transport and regional scale air mass modification processes. For example, integrated O3 abundance below 5-km altitude averaged 40% and 30% greater in air masses influenced by anthropogenic sources and biomass burning, respectively, than in background (polar) air. Conversely, aged air transported from subtropical areas of the Pacific at times reduced O3 abundance in this height interval by up to 20%. Though intrusion of anthropogenic air was infrequent during the experiment period, the influence of biomass-burning emissions was particularly notable as two thirds of the flights sampled air influenced by plumes from fires burning in Alaska and western Canada. The impinging pollution, both natural and anthropogenic, not only elevated O3 levels directly but also was a source of reactive nitrogen (and nonmethane hydrocarbons) which generally increases the tropospheric lifetime of O3 via moderation of photochemical destruction rates.

Anderson, B. E.↗

Nimbus-7 Total Ozone Mapping Spectrometer (TOMS) Data Products User's Guide

Two data products from the Total Ozone Mapping Spectrometer (TOMS) onboard Nimbus-7 have been archived at the Distributed Active Archive Center, in the form of Hierarchical Data Format files. The instrument measures backscattered Earth radiance and incoming solar irradiance; their ratio is used in ozone retrievals. Changes in the instrument sensitivity are monitored by a spectral discrimination technique using measurements of the intrinsically stable wavelength dependence of derived surface reflectivity. The algorithm to retrieve total column ozone compares measured Earth radiances at sets of three wavelengths with radiances calculated for different total ozone values, solar zenith angles, and optical paths. The initial error in the absolute scale for TOMS total ozone is 3 percent, the one standard deviation random error is 2 percent, and drift is less than 1.0 percent per decade. The Level-2 product contains the measured radiances, the derived total ozone amount, and reflectivity information for each scan position. The Level-3 product contains daily total ozone amount and reflectivity in a I - degree latitude by 1.25 degrees longitude grid. The Level-3 product also is available on CD-ROM. Detailed descriptions of both HDF data files and the CD-ROM product are provided.

McPeters, Richard D.↗

Evaluating Ultraviolet Radiation Exposures Determined from TOMS Satellite Data at Sites of Amphibian Declines in Central and South America

Many amphibian species have experienced substantial population declines, or have disappeared altogether, during the last several decades at a number of amphibian census sites in Central and South America. This study addresses the use of satellite-derived trends in solar ultraviolet-B (UV-B; 280-320 nm) radiation exposures at these sites over the last two decades, and is intended to demonstrate a role for satellite observations in determining whether UV-B radiation is a contributing factor in amphibian declines. UV-B radiation levels at the Earth's surface were derived from the Total Ozone Mapping Spectrometer (TOMS) satellite data, typically acquired daily since 1979. These data were used to calculate the daily erythemal (sunburning) UV-B, or UV-B(sub ery), exposures at the latitude, longitude, and elevation of each of 20 census sites. The annually averaged UV-B(sub ery) dose, as well as the maximum values, have been increasing in both Central and South America, with higher levels received at the Central American sites. The annually averaged UV-B(sub ery) exposures increased significantly from 1979-1998 at all 11 Central American sites examined (r(exp 2) = 0.60 - 0.79; P<=0.015), with smaller but significant increases at five of the nine South American sites (r(exp 2) = 0.24-0.42; P<=0.05). The contribution of the highest UV-B(sub ery) exposure levels (>= 6750 J/sq m*d) to the annual UV-B(sub ery) total has increased from approx. 5% to approx. 15% in Central America over the 19 year period, but actual daily exposures for each species are unknown. Synergy among UV-B radiation and other factors, especially those associated with alterations of water chemistry (e.g., acidification) in aqueous habitats is discussed. These findings justify further research concerning whether UV-B(sub ery) radiation plays a role in amphibian population declines and extinctions.

Middleton, Elizabeth M.↗