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At least 19 records

How do drought and heat affect the response of soybean seed yield to elevated O3? An analysis of 15 seasons of free-air O3 concentration enrichment (O3-FACE) studies

Over the past 15 years, soybean seed yield response to season-long elevated O3 concentrations [O3] and to year-to-year weather conditions was studied using free-air O3 concentration enrichment (O3-FACE) in the field at the SoyFACE facility in Central Illinois. Elevated [O3] significantly reduced seed yield across cultivars and years. However, our results quantitatively demonstrate that weather conditions, including soil water availability and air temperature, did not alter yield sensitivity to elevated [O3] in soybean.

drought, elevated O3, heat, O3-FACE, soybean, yiel↗

Double-quantum vibrational energy transfer in the O3-CO and O3-OCS systems

Using the CO2 laser induced fluorescence technique at 298 K for excitation of the P(30) transition in O3 or the P(22) transition in OCS, double-quantum vibrational energy transfer was studied in the O3-CO and O3-OCS binary gas systems. Rapid rates were observed for energy transfer from the CO (nu = 1) to the coupled O3(200), O3(101), and O3(002) levels, as well as for the transfer from the coupled O3(001) and O3(100) levels to the OCS(020) level. Deactivation of OCS by N2, Ar, and OCS was studied and deactivation rate constants were measured. The experimental results are compared with those calculated using the first order perturbation theory of dipole transition-moment interactions (Sharma and Brau, 1969) as modified by Tam (1972). An attempt is made to interpret the obtained results.

Hui, K.-K.↗

Reaction rates for O3 + HCl yielding O + O2 + HCl, Cl + O3 yielding ClO + O2, and HCl + O yielding OH + Cl at elevated temperatures

Ozone and a much greater quantity of hydrogen chloride, slightly diluted by oxygen and argon, were heated by a shock wave process to temperatures in the range 480-1300 K at pressures from four to eight atmospheres. From variations in ozone concentration, determined by the attentuation of 2537-A radiation, the rate coefficient for the reaction O3 + HCl yielding O + O2 + HCl was determined to be k1 = (4.0 plus or minus 1.5) x 10 to the minus 10 exp(-10,408/T)cm3/s for temperatures of 480-720 K. From the concentration of ClO remaining at the end of ozone decomposition the rate coefficients for the reactions Cl + O3 yielding ClO + O2 and HCl + O yielding OH + Cl were also deduced for a temperature of about 1100 K.

Park, C.↗

Joint Assimilation of Surface, GEO, and LEO CO, NO2, and O3 In Situ and Partial Column/Profile Retrievals with WRF-Chem/DART

Low earth orbiting (LEO) satellites like OMI or TROPOMI and geostationary satellites like TEMPO (to be launched January 2023) provide ozone (O3) retrieval profiles that extend into the stratosphere. Regional models like WRF-Chem generally do not include the stratosphere and have vertical grids that end near the tropopause. This causes difficulties when assimilating O3 retrievals (both column and profile retrievals) because the respective observation forward operators require model O3 profiles that extend into the stratosphere. In this presentation, we look at results from assimilating O3 observation from surface (in situ measurements), multiple LEO (profile retrievals), and GEO (proxy profile retrievals) platforms in as regional model where we use a global chemical transport model (GCTM) to provide O3 upper boundary conditions (BCs) to enable application of the O3 observation forward operators. We will also present results from assimilating O3 retrievals together with carbon monoxide (CO) observations from surface (in situ measurements) and multiple LEO platforms (column and profile retrievals), and nitrogen dioxide (NO2) observations from surface (in situ measurements), multiple LEO (column retrievals), and GEO (proxy column retrievals) platforms. Our joint assimilation experiments show that sometimes the observations complement each, e.g., when assimilating surface and satellite CO or NO2 observations, and sometimes the observations conflict with each other, e.g., when assimilating observations that are biased with respect to other observations (e.g., CO retrievals), or when the assimilation increments conflict due to their chemical interaction (e.g., surface O3 and NO2 retrievals). Results from assimilation of O3 retrieval profiles in regional model are preliminary and will also be discussed in our presentation. Our expectation is that using GCTM O3 as upper BCs in the regional model for evaluation of the O3 forward operator will improve our O3 forecasts. In summary, we will present results from jointly assimilating surface, LEO, and GEO CO, NO2, and O3 in situ and satellite observations in a regional model with dynamic emissions estimation. This study uses proxy GEO observations as a prelude to actual observations because the GEO platform will not be launched until after our presentation.

WRF-Chem/DART↗

Photolysis of Pure Solid O3 and O2 Films at 193nm

We studied quantitatively the photochemistry of solid O3 and O2 films at 193 nm and 22 K with infrared spectroscopy and microgravimetry. Photolysis of pure ozone destroyed O3, but a small amount of ozone remained in the film at high fluence. Photolysis of pure O2 produced O3 in an amount that increased with photon fluence to a stationary level. For both O2 and O3 films, the O3:O2 ratio at large fluences is ?0.07, about two orders of magnitude larger than those obtained in gas phase photolysis. This enhancement is attributed to the increased photodissociation of O2 due to photoabsorption by O2 dimers, a process significant at solid-state densities. We obtain initial quantum yield for ozone synthesis from solid oxygen, phi (O3) = 0.24 0.06, and quantum yields for destruction of O3 and O2 in their parent solids, phi(-O3) = 1.0 0.2 and phi(-O2) = 0.36 0.1. Combined with known photoabsorption cross sections, we estimate probabilities for geminate recombination of 0.5 0.1 for O3 fragments and 0.88 0.03 for oxygen atoms from O2 dissociation. Using a single parameter kinetic model, we deduce the ratio of reaction cross sections for an O atom with O2 vs. O3 to be 0.1 0.2. The general good agreement of the model with the data suggests the validity of the central assumption of efficient energy and spin relaxation of photofragments in the solid prior to their reactions with other species.

Raut, U.↗

The variations of CO and O3 concentrations in a region subject to biomass burning

Carbon monoxide (CO) and ozone (O3) concentrations have been observed in the Brazilian Amazon region, at a site strongly affected by biomass burning (Cuiaba, 16 deg S, 58 deg W). Time variations are described for the first long-term program of studying the effect of biomass burning on O3 and CO over a complete seasonal cycle, including the seasonal maxima of 1987 and 1988. In order to obtain elements for comparison, an identical observational program was maintained at a site totally outside of the direct influence of biomass burning (Natal, 6 deg S, 35 deg W). The biomass burning contribution to the Cuiaba concentrations of CO and O3 is very large. Diurnal maxima concentrations exceeded 90 ppbv O3 in 1987 and 120 ppbv O3 in 1988, in September. For the wet season, the monthly average ozone concentration in March-April is about 10 ppbv. During the month of maxima, September, the O3 concentration average was 41 ppbv for 1987 and 71 ppbv for 1988. The CO concentrations are about 90 ppbv in the wet season. In September, 460 ppbv and 660 ppbv of CO were observed for 1987 and 1988, respectively. At Natal the seasonal variation is of the order of a factor of 2. During the wet season, the concentrations of CO and O3 at both stations are about the same.

Kirchhoff, V. W. J. H.↗

Lidar Observations Revealing Transport of O3 in the Presence of a Nocturnal Low-Level Jet: Regional Implications for "Next-Day" Pollution

Remotely sensed profiles of ozone (O3) and wind are presented continuously for the first time during anocturnal low-level jet (NLLJ) event occurring after a severe O3 episode in the Baltimore-Washington D.C.(BW) urban corridor throughout 11-12 June 2015. High-resolution O3 lidar observations indicate a well mixedand polluted daytime O3 reservoir, which decayed into a contaminated nocturnal residual layer(RL) with concentrations between 70 and 100 ppbv near 1 km above the surface. Observations indicatethe onset of the NLLJ was responsible for transporting polluted O3 away from the region, while simultaneouslyaffecting the height and location of the nocturnal residual layer. High-resolution modelinganalyses and next-day (12 June) lidar, surface, and balloon-borne observations indicate the trajectory ofthe NLLJ and polluted residual layer corresponds with ''next-day'' high O3 at sites throughout thesouthern New England region (New York, Connecticut, Massachusetts). The novel O3 lidar observationsare evidence of both nocturnal advection (via high NLLJ wind fields) and entrainment of the pollutedresidual layer in the presence of the ''next-day'' convectively growing boundary layer. In the greatercontext, the novel observational suite described in this work has shown that the chemical budget in areasdownwind of major urban centers can be altered significantly overnight during transport events such asthe NLLJ.

ozone↗

Representativeness of CO and O3 Along ATom Transects Derived from GEOS-5 and GMI-CTM Simulations

One major goal for the NASA Atmospheric Tomography Mission (ATom) is producing an observation-based chemical climatology to represent the atmospheric heterogeneity. In this study, we use CO and O3 observations and global atmospheric model simulations to examine the spatial representativeness of the ATom-1 and -2 transects within a 4D framework provided by the NASA GEOS-5 and GMI-CTM models. Based on the probability density functions, we find that the variability of CO and O3 along the flight tracks is well hindcast by the model when sampled per ATom flights. The CO variations along the ATom-transect are likely representative of the typical CO variations over the whole Pacific basin during both the ATom-1 and -2 periods, the northern Atlantic during the ATom-1 period, and the tropical Atlantic in the ATom-2 period. Over southern Atlantic, CO along the ATom-1 transects is likely less well mixed than that of the broader region, but is still representative of the median CO concentration. CO along the ATom-2 transect is likely higher than the median CO concentration over this region. For O3, the agreements between PDFs of O3 sampled along the ATom transects and over the broader regions are fair to good over all six regions (Scores > 0.65) with notable discrepancies over some regions. For example, in ATom-1 over the northern Pacific and Atlantic, the transect samples air masses with higher O3 levels. During ATom-2, the transect over-represents the occurrence of O3 plumes over tropical Pacific. Over the southern Pacific and Atlantic for both ATom-1 and -2, the transects have a less uniform distribution compared to the surrounding basins, but still represent the median O3 abundance. Overall, we conclude in most cases that ATom measurements represent the statistical variations of these two species over the ocean basins at the time of measurement. Higher-order statistics, including covariance of species, has not been tested in this study.

ozone↗

Reactions of CH3, CH3O, and CH3O2 radicals with O3

Ozone was photolyzed at 253.7 nm at 25 and -52 degrees in the presence of CH4 and O2 to measure the reactions of O3 with CH3, CH3O, and CH3O2. The O(1D) atoms produced in the primary photochemical act react with CH4 to give CH3 radicals which in turn can react with O2 to give CH3O2 and CH3O radicals. At very high O2 to O3 concentration ratios, the quantum yield of O3 disappearance approached 1.0, indicating that O3 reactions with CH3O2 and CH3O are slow. Upper limits to the rate coefficients at 25 degrees were computed. At lower values of the concentration ratio, chain decomposition of O3 occurred which could be explained by the reaction of O3 with CH3 radicals to produce CH2O, O2, and H atoms all the time. The two routes to these products are considered, and the preferred reaction channel is found.

Simonaitis, R.↗

Global Multi-Year O3-CO Correlation Patterns from Models and TES Satellite Observations

The correlation between measured tropospheric ozone (O3) and carbon monoxide (CO) has been used extensively in tropospheric chemistry studies to explore the photochemical characteristics of different regions and to evaluate the ability of models to capture these characteristics. Here, we present the first study that uses multi-year, global, vertically resolved, simultaneous and collocated O3 and CO satellite (Tropospheric Emission Spectrometer) measurements, to determine this correlation in the middle/lower free troposphere for two different seasons, and to evaluate two chemistry-climate models. We find results that are fairly robust across different years, altitudes and timescales considered, which indicates that the correlation maps presented here could be used in future model evaluations. The highest positive correlations (around 0.8) are found in the northern Pacific during summer, which is a common feature in the observations and the G-PUCCINI model. We make quantitative comparisons between the models using a single-figure metric (C), which we define as the correlation coefficient between the modeled and the observed O3-CO correlations for different regions of the globe. On a global scale, the G-PUCCINI model shows a good performance in the summer (C =0.71) and a satisfactory performance in the winter (C = 0.52). It captures midlatitude features very well, especially in the summer, whereas the performance in regions like South America or Central Africa is weaker. The UKCA model (C = 0.46/0.15 for July-August/December-January on a global scale) performs better in certain regions, such as the tropics in winter, and it captures some of the broad characteristics of summer extratropical correlations, but it systematically underestimates the O3-CO correlations over much of the globe. It is noteworthy that the correlations look very different in the two models, even though the ozone distributions are similar. This demonstrates that this technique provides a powerful global constraint for understanding modeled tropospheric chemical processes. We investigated the sources of the correlations by performing a series of sensitivity experiments. In these, the sign of the correlation is, in most cases, insensitive to removing different individual emissions, but its magnitude changes downwind of emission regions when applying such perturbations. Interestingly, we find that the O3-CO correlation does not solely reflect the strength of O3 photochemical production, as often assumed by earlier studies, but is more complicated and may reflect a mixture of different processes such as transport.

Voulgarakis, A.↗

Intermode energy transfer in vibrationally excited O3

The laser-excited fluorescence method has been employed to determine the rate constants for vibrational relaxation of the O3 (010), O3 (100) and O3 (001) levels at 298 K. The fluorescence observations from the O3 (010) level provide direct measurements of the rate for intermode vibrational energy transfer from the coupled nu sub 1 and nu sub 3 modes to the nu sub 2 mode. The slowness of this process indicates the likelihood that the nu sub 1 and/or nu sub 3 modes (rather than the nu sub 2 mode) play a predominant role in the laser-enhanced reaction between vibrationally excited O3 and NO at 298 K.

Hui, K.-K.↗

Emission of NO and deposition of O3 in a tropical forest system

Rates for emission of NO and deposition of O3 were measured at a tropical forest site in Reserve Adolfo Ducke, near Manaus, Brazil. Two independent techniques were used to determine the NO flux: (1) a soil enclosure method and (2) a method based on simultaneous observations of NO and O3 vertical profiles at night, when NO is irreversibly removed by reaction with O3. Results obtained using the two techniques agreed well, giving an average NO flux of 5.2 + or - 1.7 x 10 to the 10th molecules/sq cm per sec and an average vertical exchange coefficient of 2.2 x 10 to the 3rd cu cm/sec. Sources of NO from tropical forest soils may be important for global atmospheric chemistry. Rapid removal of O3 was observed in the lowest levels of the forest. The nocturnal deposition rate was estimated to be 5.6 + or - 2.5 x 10 to the 11th molecules/sq cm per sec through the 6-m level. The large deposition rate for O3 is consistent with the strong sink inferred from observations of ozone in the Amazon region.

Kaplan, W. A.↗

Non-local thermodynamic equilibrium limb radiance from O3 and CO2 in the 9-11 micrometer spectral region

Satellite remote sensing of mesospheric and thermospheric O3 abundance in the terrestrial atmosphere often uses 9-11 micrometer thermal emission. In this paper, we apply a line-by-line non-local thermodynamic equilibrium (non-LTE) radiance model to this spectral region and investigate the conditions of LTE breakdown and the effect that this has on the limb radiance measured by an i.r. sounder. Monochromatic and band-integrated radiance calculations have been performed for limb view tangent heights between 55 and 105 km under daytime and nighttime conditions. Non-LTE emission from both O3 and CO2 are shown to be important with the divergence of radiance from LTE values and the diurnal variation being band dependent. We have shown that the contribution of the CO2 bands to the Limb Infrared Monitor of the Stratosphere O3 channel is significant for daytime conditions at tangent heights above about 60 km. A study has been made to choose O3 sounding channel spectral passbands for the High Resolution Dynamics Limb Sounder. High resolution calculations are required to determine those spectral intervals that will filter radiance from selected bands and characterize their non-LTE behavior. This will allow for improved O3 retrievals above 70 km and non-LTE studies.

Edwards, David P.↗

Reactive Nitrogen and its Correlation with O3 and CO Over the Pacific in Winter and Early Spring

Measurements of NO, NO(y), O3, and CO were made during NASA's Global Tropospheric Experiment/Pacific Exploratory Mission-West B (GTE/PEM-West B) carried out over the western Pacific in February and March 1994. NO(x) was calculated from NO using a photostationary state model ((NO(x)(sub mc)). Correlations between these species are presented, and some insights into the sources of NO(x) and NO(y) are described. The boundaries between the lower, middle, and upper troposphere have been defined at potential temperatures of 311 K and 328 K, which correspond to the geometric altitudes of about 5 and 9 km at 30degN. Enhancements in the mixing ratios of NO(y) and CO were observed in the lower and middle troposphere. A positive correlation was found between these two species suggesting that the high NO(y) values were due to anthropogenic emissions over the continental surface. On the other hand, O3 increased little with increase in CO. As a result, NO(y)/O3 ratios were higher in air more influenced by pollution. NO(y), values in 55 and 28% of the air masses sampled in the lower and middle troposphere, respectively, were higher than the clean free tropospheric NO(y)-O3 range when O3 values simultaneously observed were used. High (NOx)mc/NOy ratios between 0.15 and 0.3 were found in the boundary layer with relatively low mixing ratios of CO and NOy during the three flights. These air masses were transported from a higher altitude (approximately 5 km) and a higher latitude (approximately 50degN) within a few days. The peroxyacetyl nitrate (PAN)/NO(y) ratios were generally high (approximately 0.4) in these air masses, and the thermal decomposition of PAN was a probable source of NO(x). In the middle troposphere the (NO(x))mc mixing ratio did not generally increase with NO(y) or CO, suggesting that the transport of air masses affected by anthropogenic emissions did not increase the NO(x) level significantly. In the upper troposphere, very minor effects from the continental surface sources were seen in the CO mixing ratio. By contrast, NO(y) values in 33% of the air masses were higher than those expected when stratospheric air intrusion is assumed to be a single source of NO(y) based on NO(y)-O3 correlation analyses. This result suggests significant free tropospheric NO(y) sources, namely exhaust from the aircraft and NO production by lightning activity. In fact, spikes in the (NO(x))(sub m)c mixing ratios were observed near the aircraft corridor south of Tokyo at an altitude of 10 km. These two free tropospheric NO(x) sources were considered to be important in determining the levels of the upper tropospheric NO(x) and NO(y) during PEM-West B.

Koike, M.↗

Establishing the Dependence of [HO2]/[OH] on Temperature, Halogen Loading, O3, and NO(x) Based on in Situ Measurements from the NASA ER-2

In situ observations of OH and HO2 from the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA), Stratospheric TRacers of Atmospheric Transport (STRAT), and Polar Ozone Loss in the Arctic Region in Summer (POLARIS) NASA ER-2 field campaigns are used to examine the partitioning of HO(x) in the lower stratosphere (tropopause to approx.21 km) and upper troposphere (approx.10 km to tropopause). These measurements span a latitude range from 70degS to 90degN and a variety of atmospheric conditions as a result of seasonal changes and altitude. The response of the observed [HO2]/[OH] to changes in temperature, [03], [CO], [NO], [CIO], and [BrO] is investigated. The measured ratio is accurately described (approx.+/-10%) by a steady-state model constrained by the measured mixing ratios of O3, CO, NO, CIO, and BrO, where the model is valid for conditions of HO(x) cycling much faster than HO(x) production and loss. The concentration of HO2 depends on [OH], which, to first order, has been observed to be a simple function of the solar zenith angle in the lower stratosphere. The partitioning between OH and HO2 is controlled by the local chemistry between the HO, radicals and O3, CO, NO, CIO, and BrO. The response of [HO(x)] to changes in [NO(x)] and [O3] is demonstrated. Further observations are necessary to illustrate the response of HO(x) to changes in halogen concentrations. A quantitative understanding of [HO2]/[OH] is important, since many of the reactions that control this ratio are directly involved in catalytic removal of O3 in the lower stratosphere and production of O3 in the upper troposphere.

Lanzendorf, E. J.↗

Spatial and Temporal Variability of Ground and Satellite Column Measurements of NO2 and O3 over the Atlantic Ocean During the Deposition of Atmospheric Nitrogen to Coastal Ecosystems Experiment

In situ measurements of O3 and nitrogen oxides (NO + NO2=NOx) and remote sensing measurements of total column NO2 and O3 were collected on a ship in the North Atlantic Ocean as part of the Deposition of Atmospheric Nitrogen to Coastal Ecosystems (DANCE) campaign in July August 2014,100 km east of the mid-Atlantic United States. Relatively clean conditions for both surface in situ mixing ratio and total column O3 and NO2 measurements were observed throughout the campaign. Increased surface and column NO2 and O3 amounts were observed when a terrestrial air mass was advected over the study region. Relative to ship-based total column measurements using a Pandora over the entire study, satellite measurements overestimated total column NO2 under these relatively clean atmospheric conditions over offshore waters by an average of 16. Differences are most likely due to proximity, or lack thereof, to surface emissions; spatial averaging due to the field of view of the satellite instrument; and the lack of sensitivity of satellite measurements to the surface concentrations of pollutants. Total column O3 measurements from the shipboard Pandora showed good correlation with the satellite measurements(r 0.96), but satellite measurements were 3 systematically higher than the ship measurements, in agreement with previous studies. Derived values of boundary layer height using the surface in situ and total column measurements of NO2 are much lower than modeled and satellite-retrieved boundary layer heights, which highlight the differences in the vertical distribution between terrestrial and marine environments.

Martins, Douglas K.↗