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The atmospheric absorption features of over 500 infrared solar spectra recorded at McMurdo Station have been analyzed to determine the vertical column abundances of trace gases crucial to understanding of the 'ozone hole' phenomenon. The techniques used to retrieve the column abundances are described. Results are reported for ozone, nitrogen species, and halogen sinks and reservoirs.
Ozone retrievals from Stratospheric Aerosol and Gas Experiment (SAGE) II version 5.96 (v5.96) below approx. 25 km altitude are discussed. This version of the algorithm includes improved constraints on the wavelength dependence of aerosol extinctions based on the ensemble of aerosol size distribution measurements. This results in a reduction of SAGE ozone errors in the 2 years after the Mount Pinatubo eruption. However, SAGE ozone concentrations are still approx. 10% larger than ozonesonde and Halogen Occultation Experiment (HALOE) measurements below 20 km altitude under nonvolcanic conditions (and by more than this in the tropics). The analysis by Steele and Turco suggests that the SAGE ozone overpredictions are in the wrong direction to be explained by aerosol extinction extrapolation errors. Moreover, preliminary SAGE 11 v6.0a retrievals suggest that they are partially accounted for by geometric difficulties at low altitudes in v5.96 and prior retrievals. SAGE ozone trends for the 1979-1996 and 1984-1996 periods are calculated and compared, and the sources of trend errors are discussed. These calculations are made after filtering out ozone data during periods of high, local aerosol extinctions. In the lower stratosphere, below approx. 28 km altitude, there is shown to be excellent agreement in the altitudinal structure of ozone decreases at 45 deg N between SAGE and ozonesondes with the largest decrease in both between 1979 and 1996 having occurred below 20 km altitude, amounting to 0.9 +/- 0.7% yr (2sigma) at 16 km altitude. However, in contrast to the fairly steady decreases at 45 deg N, both SAGE measurements and Lauder ozonesondes show ozone increases at 45 deg S over the period from the mid-1980s to 1996 of 0.2 +/- 0.5%/yr (2sigma) from 15 to 20 km altitude. The SAGE data suggest that this increase is a wintertime phenomenon which occurs in the 15-20 km height range. Changes in dynamics are suggested as the most likely cause of this increase. These hemispheric differences in ozone trends are supported by ozone column measurements by the Total Ozone Mapping Spectrometer (TOMS).
We examine the tropical ozone mixing ratio perturbation fields generated from a monthly ozone climatology using 1998 to 2006 ozonesonde data from the Southern Hemisphere Additional Ozonesondes (SHADOZ) network and the 13-year satellite record from 1993 to 2005 obtained from the Halogen Occultation Experiment (HALOE). The long time series and high vertical resolution of the ozone and temperature profiles from the SHADOZ sondes coupled with good tropical coverage north and south of the equator gives a detailed picture of the ozone structure in the lowermost stratosphere down through the tropopause where the picture obtained from HALOE measurements is blurred by coarse vertical resolution. Ozone perturbations respond to annual variations in the Brewer-Dobson Circulation (BDC) in the region just above the cold-point tropopause to around 20 km. Annual cycles in ozone and temperature are well correlated. Above 20 km, ozone and temperature perturbations are dominated by the Quasi-biennial Oscillation (QBO). Both satellite and sonde records show good agreement between positive and negative ozone mixing ratio anomalies and alternating QBO westerly and easterly wind shears from the Singapore rawinsondes with a mean periodicity of 26 months for SHADOZ and 25 months for HALOE. There is a temporal offset of one to three months with the QBO wind shear ahead of the ozone anomaly field. The meridional length scales for the annual cycle and the QBO, obtained using the temperature anomalies and wind shears in the thermal wind equation, compare well with theoretical calculations.
An ozone simulation from the Goddard three-dimensional chemistry and transport model for the 1995-96 northern hemisphere winter is compared with ozone observations from airborne Differential Absorption Lidar (DIAL), from the Polar Ozone and Aerosol Measurement (POAM), from the Microwave Limb Sounder (MLS), and from the Halogen Occultation Experiment (HALOE). The 3D model uses winds from the Goddard Data Assimilation System. The 3D model reproduces the latitude dependence of the horizontal and vertical ozone gradients of the subtropical DIAL observations. Comparisons with subtropical satellite observations, which lack the spatial resolution of DIAL but provide near continuous coverage throughout the subtropics, show that the model also reproduces longitude and temporal dependence in the tropical-midlatitude boundary. At polar latitudes, observations from DIAL flights on December 9 and January 30, and POAM and MLS between late December and late January are compared with the 3D model. Data from the three platforms consistently show that the observed ozone has a negative trend relative to the modeled ozone, and that the trend is uniform in time between early and mid winter, with no obvious dependence on proximity to the vortex edge.
We present a study of the distribution of ozone in the lowermost stratosphere with the goal of understanding the relative contribution to the observations of air of either distinctly tropospheric or stratospheric origin. The air in the lowermost stratosphere is divided into two population groups based on Ertel's potential vorticity at 300 hPa. High [low] potential vorticity at 300 hPa suggests that the tropopause is low [high], and the identification of the two groups helps to account for dynamic variability. Conditional probability distribution functions are used to define the statistics of the mix from both observations and model simulations. Two data sources are chosen. First, several years of ozonesonde observations are used to exploit the high vertical resolution. Second, observations made by the Halogen Occultation Experiment [HALOE] on the Upper Atmosphere Research Satellite [UARS] are used to understand the impact on the results of the spatial limitations of the ozonesonde network. The conditional probability distribution functions are calculated at a series of potential temperature surfaces spanning the domain from the midlatitude tropopause to surfaces higher than the mean tropical tropopause [about 380K]. Despite the differences in spatial and temporal sampling, the probability distribution functions are similar for the two data sources. Comparisons with the model demonstrate that the model maintains a mix of air in the lowermost stratosphere similar to the observations. The model also simulates a realistic annual cycle. By using the model, possible mechanisms for the maintenance of mix of air in the lowermost stratosphere are revealed. The relevance of the results to the assessment of the environmental impact of aircraft effluence is discussed.
We present a study of the distribution of ozone in the lowermost stratosphere with the goal of understanding the relative contribution to the observations of air of either distinctly tropospheric or stratospheric origin. The air in the lowermost stratosphere is divided into two population groups based on Ertel's potential vorticity at 300 hPa. High [low] potential vorticity at 300 hPa suggests that the tropopause is low [high], and the identification of the two groups helps to account for dynamic variability. Conditional probability distribution functions are used to define the statistics of the mix from both observations and model simulations. Two data sources are chosen. First, several years of ozonesonde observations are used to exploit the high vertical resolution. Second, observations made by the Halogen Occultation Experiment [HALOE) on the Upper Atmosphere Research Satellite [UARS] are used to understand the impact on the results of the spatial limitations of the ozonesonde network. The conditional probability distribution functions are calculated at a series of potential temperature surfaces spanning the domain from the midlatitude tropopause to surfaces higher than the mean tropical tropopause [approximately 380K]. Despite the differences in spatial and temporal sampling, the probability distribution functions are similar for the two data sources. Comparisons with the model demonstrate that the model maintains a mix of air in the lowermost stratosphere similar to the observations. The model also simulates a realistic annual cycle. By using the model, possible mechanisms for the maintenance of mix of air in the lowermost stratosphere are revealed. The relevance of the results to the assessment of the environmental impact of aircraft effluence is discussed.
We present a study of the distribution of ozone in the lowermost stratosphere with the goal of characterizing the observed variability. The air in the lowermost stratosphere is divided into two population groups based on Ertel's potential vorticity at 300 hPa. High (low) potential vorticity at 300 hPa indicates that the tropopause is low (high), and the identification of these two groups is made to account for the dynamic variability. Conditional probability distribution functions are used to define the statistics of the ozone distribution from both observations and a three-dimensional model simulation using winds from the Goddard Earth Observing System Data Assimilation System for transport. Ozone data sets include ozonesonde observations from northern midlatitude stations (1991-96) and midlatitude observations made by the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS) (1994- 1998). The conditional probability distribution functions are calculated at a series of potential temperature surfaces spanning the domain from the midlatitude tropopause to surfaces higher than the mean tropical tropopause (approximately 380K). The probability distribution functions are similar for the two data sources, despite differences in horizontal and vertical resolution and spatial and temporal sampling. Comparisons with the model demonstrate that the model maintains a mix of air in the lowermost stratosphere similar to the observations. The model also simulates a realistic annual cycle. Results show that during summer, much of the observed variability is explained by the height of the tropopause. During the winter and spring, when the tropopause fluctuations are larger, less of the variability is explained by tropopause height. This suggests that more mixing occurs during these seasons. During all seasons, there is a transition zone near the tropopause that contains air characteristic of both the troposphere and the stratosphere. The relevance of the results to the assessment of the environmental impact of aircraft effluence is also discussed.
We investigated water vapor variations in the tropical lower stratosphere on seasonal, quasi-biennial oscillation (QBO), and decadal time scales using balloon-borne cryogenic frost point hygrometer data taken between 1993 and 2009 during various campaigns including the Central Equatorial Pacific Experiment (March 1993), campaigns once or twice annually during the Soundings of Ozone and Water in the Equatorial Region (SOWER) project in the eastern Pacific (1998-2003) and in the western Pacific and Southeast Asia (2001-2009), and the Ticosonde campaigns and regular sounding at Costa Rica (2005-2009). Quasi-regular sounding data taken at Costa Rica clearly show the tape recorder signal. The observed ascent rates agree well with the ones from the Halogen Occultation Experiment (HALOE) satellite sensor. Average profiles from the recent five SOWER campaigns in the equatorial western, Pacific in northern winter and from the three Ticosonde campaigns at Costa Rica (10degN) in northern summer clearly show two effects of the QBO. One is the vertical displacement of water vapor profiles associated with the QBO meridional circulation anomalies, and the other is the concentration variations associated with the QBO tropopause temperature variations. Time series of cryogenic frost point hygrometer data averaged in a lower stratospheric layer together with HALOE and Aura Microwave Limb Sounder data show the existence of decadal variations: The mixing ratios were higher and increasing in the 1990s, lower in the early 2000s, and probably slightly higher again or recovering after 2004. Thus linear trend analysis is not appropriate to investigate the behavior of the tropical lower stratospheric water vapor.
The April 2002 solar storm event provides a unique opportunity to study the resulting effects on upper atmospheric constituents such as NO and O3. Two sources may perturb these constituents. For a magnetic-storm-source, energetic particles collide with and dissociate N2 in the lower thermosphere to produce excited nitrogen atoms which then combine with O to produce NO. The NO subsequently is transported down to lower altitudes where it reacts with and thus destroys mesospheric and possibly stratospheric ozone. For a solar-particle-event-source, high energy particles penetrate directly into the mesosphere, break apart N2 and water vapor, creating NOx and HOx to destroy ozone in the middle atmosphere. We present perturbations in high northern latitude NO and O3 as measured by the Halogen Occultation Experiment (HALOE) aboard the Upper Atmosphere Research Satellite between April 20-27. HALOE observations show an order of magnitude increase in mesospheric NO and a factor of approximately 2 decrease in mesospheric O3. We will also compare these observations with NASA GSFC 2D model computations.
Results form modeling studies of the Antarctic lower stratosphere which have attempted to simulate the large springtime ozone losses and corresponding changes in other trace constituents are given. These studies were carried out in a photochemical box model, a one-dimensional model without transport and in a two-dimensional photochemical-dynamical-radiation model. The photochemical studies have investigated inter alia the sensitivity of ozone to inclusion in the model of heterogeneous chemistry, and to the inclusion of the ClO dimer. When both of these are incorporated in the model, ozone depletions resembling whose found in Halley Bay in 1987 (J.C. Farman, Nature, 329, 1987) can be reproduced. The temporal variations (both diurnal and during the August to October period) of a number of important tracers including HCl, ClONO2, OClO and BrO are discussed. The two-dimensional study concentrated on the difficulty of establishing in the model the dynamical preconditioning of the lower polar stratosphere - low temperatures, low N2O, etc., high ClOx. Calculations are presented to show: (1) the depletion of ozone during the springtime season, (2) the effect of large ozone losses on lower latitudes, and (3) the longer term (multi-year) variations of ozone in Antarctica, assuming realistic increases in the atmospheric halogen burden.
The recent ban on the production of bromotrifluoromethane (CF3Br) because of its high stratospheric ozone depletion potential has led to interest in finding alternative agents for fire extinguishing applications. Some of the promising alternatives are fluorinated hydrocarbons. A clear understanding of the effects of CF3Br and alternative chemical suppressants on diffusion flames is therefore necessary in the selection of alternative suppressants for use in normal and microgravity. The flame inhibition effects of halogen compounds have been studied extensively in premixed systems. The effect of addition of halocarbons (carbon-halogen compounds) to diffusion flames has been studied experimentally in coflow configurations and in counterflow gaseous and liquid-pool flames. Halogenated compounds are believed to inhibit combustion by scavenging hydrogen radicals to form the relatively unreactive compound HF, or through a catalytic recombination cycle involving HBr to form H2. Comparisons between halogens show that bromine inhibition is significantly more effective than chlorine or fluorine. Although fluorinated compounds are only slightly more effective inhibitors on a mass basis than nitrogen, they are more effective on a volume basis and are easily stored in liquid form. The objectives of this study are (a) to determine the stability limits of laminar jet diffusion flames with respect to inhibitor concentration in both normal and microgravity, and (b) to investigate the structure of halocarbon-inhibited flames. In the initial phase of this project, visual diagnostics were used to observe the structure and behavior of normal and microgravity flames. The initial observations showed significant changes in the structure of the flames with the addition of halocarbons to the surrounding environment, as discussed below. Furthermore, the study established that the flames are more stable relative to the addition of halocarbons in microgravity than in normal gravity. Visual diagnostics of flames are, however, necessarily limited to detection of radiative emission in the visible range, and offer only qualitative information about the nature of the processes in the flame. In particular, the study sought to understand the structure of the inhibitor-perturbed flames with regard to temperature and species concentration in the outer region of the flame. Whereas thermocouple measurements can be used in ground based studies, their implementation in drop-tower rigs is limited. A possible approach to determine the temperature field around the flame is to use interferometric techniques. The implementation and testing of a shear-plate interferometry technique is described below.
Precipitation of nitrate in polar stratospheric clouds (PSCs) can provide a significant sink for Antarctic stratospheric odd nitrogen. It is argued that the depth of the Ozone Hole is sensitive to the occurrence of temperatures below about 196 K. An increase in the prevalence of temperatures below 196 K would enhance ozone loss by increasing the spatial extent and persistence of PSCs, and by decreasing the level of HNO3 that remains following PSC evaporation. Concentrations of halogen gases in the 1960s and earlier were insufficient to support major ozone loss, even if thermal conditions were favorable.
One of the challenges facing atmospheric scientists is to interpret trends in multi-decadal data records. Although data records from satellite instruments are not as long as some ground-based records, global coverage and resolved vertical profiles provide unique information for identifying signatures of climate change. For example, the Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite provided profiles of O3, H2O, HC1, HF, CH4 from October 1991 until November 2005. There are also multi-annual ground based measurements of the column HCl. Middle latitude ground-based measurements show a seasonal cycle, and the HALOE profiles show that this is driven by the seasonal change in the composition and mass of the region between the tropopause and 380K surface (the lowermost stratosphere). Understanding the processes that produce the seasonal cycle makes it possible to interpret a future change in the seasonal cycle as a marker of a change in the stratospheric residual circulation. Satellite observations have also provided key information for improving the physical basis of models used to predict future composition and climate circulation. An example is the "tape recorder" signature in tropical stratospheric water vapor, i.e., the slow ascent of high and low water vapor anomalies roughly corresponding to the tropopause temperature at the time air entered the stratosphere. This signature has become a key diagnostic of performance for climate models.
Halogen species are known to catalytically destroy ozone in several regions of the atmosphere. In addition to direct catalytic losses, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr) is a key species in the linkage of BrOx to ClOx and HOx. The aqueous- phase coupling reaction HOBr + HCI (right arrow) BrCl + H2O may provide a pathway for chlorine activation on sulfate aerosols at temperatures warmer than those required for polar stratospheric cloud formation. We have measured t h e solubility of HOBr in 45 - 70 wt% sulfuric acid solutions. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, H* = 10(exp 4) - 10(exp 7) mol dm(exp -3) atm(exp -1). The expected inverse dependence of H* on temperature was observed, but only a weak dependence on acidity was found. The solubility of HOBr is comparable to that of HBr, indicating that equilibrium concentrations of HOBr could equal or exceed those of HBr in upper tropospheric and lower stratospheric aerosols. Despite the high solubility of HOBr, aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Our measurements of HOBr uptake in aqueous sulfuric acid in the presence of other brominated gases show the evolution of gaseous products including Br2O and Br2.
Solar proton events (SPEs) are known to have caused changes in constituents in the Earth's neutral polar middle atmosphere in the most recent solar maximum period (solar cycle 23). The highly energetic protons produced ionizations, excitations, dissociations, and dissociative ionizations of the background constituents in the polar cap regions (greater than 60 degrees geomagnetic latitude), which led to the production of HOx (H, OH, HO2) and NOy (N, NO, NO2, NO3, N2O5, HNO3, HO2NO2, ClONO2, BrONO2). The HOx increases led to short-lived ozone decreases in the polar mesosphere and upper stratosphere due to the short lifetimes of the HOx constituents. Polar middle mesospheric ozone decreases greater than 50% were observed and computed to last for hours to days due to the enhanced HOx. The NOy increases led to long-lived polar stratospheric ozone changes because of the long lifetime of the NOy family in this region. Upper stratospheric ozone decreases of greater than 10% were computed to last for several months past the solar events in the winter polar regions because of the enhanced NOy. Solar cycle 23 was especially replete with SPEs and huge fluxes of high energy protons occurred in July and November 2000, September and November 2001, April 2002, October 2003, and January 2005. Smaller, but still substantial, proton fluxes impacted the Earth during other months in this cycle. Observations by the Upper Atmosphere Research Satellite (UARS) Halogen Occultation Experiment (HALOE) and Solar Backscatter Ultraviolet 2 (SBUV/2) instruments along with GSFC 2D Model predictions will be shown in this talk.
Analysis of the version 16 Halogen Occultation Experiment (HALOE) CH4 data shows that this long-lived trace gas is well correlated with potential vorticity (PV) computed from National Meteorological Center balanced winds. Analyzing late September and October 1992 data, we show that very low CH4 values are confined to the interior of a vortex edge defined by the maximum gradient in PV. The CH4 and HF time tendency is used to estimate the descent rate in the Antarctic vortex. After removing a component of the trend correlated with the HALOE sampling pattern, we compute the lower stratosphere vertical descent rates and net heaing rates in the spring Antarctic vortex. Our computations of the spring Antarctic vortex heating rates give -0.5 to -0.1 K/day. Over the winter season, the overall lower stratospheric descent rate averages about 1.8-1.5 km/month. These computations are in line with radiative transfer estimates of the heating and descent rate. The HALOE data thus appear to be consistent with the picture of an isolated lower stratospheric Antarctic vortex.
Global climatic effects brought about by volcanism are related to the impact of volcanic gases and their derivative aerosols on the atmosphere, rather than the effects of volcanic ash. Evidence from both historic eruptions and polar ice cores indicate that volcanic sulfur gases are the dominant aerosol-forming component, resulting in produciton of a sulfuric acid-rich stratosphere aerosol that can have profound effects on the earth radiation budget over periods of a few years. Due to highly variable sulfur content of different magma types, the climatic effects do not relate simply to total erupted mass. There is a close relationship between volcanic sulfur yield to the atmospheric and hemispheric surface temperature decrease following an eruption, with up to 1 C surface temperature decrease indicated following a major volcanic event such as the 1815 Tambora eruption. While the erupted mass of HCl and HF is equal to or greater than that of sulfur gases in some volcanic events, the halogens do not form known aerosols nor are they abundant in ice core acidity layers. The early removal of halogens from eruption columns occurs by rain flushing and adsorption onto tephra particles, but the fate of halogens in the atmosphere following very large explosive eruptions is unknown. The CO2 flux to the atmosphere from volcanic eruptions is volumetrically one of the most important of the gas species, but owing to the huge size of the atmospheric reservoir of this gas, the volcanic contribution is likely to have negligible effects.
Tropospheric chemistry of halogens and organic carbon over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically resolved measurements of bromine monoxide (BrO), iodine monoxide (IO) and small oxygenated hydrocarbons like glyoxal (CHOCHO) in the tropical troposphere. BrO, IO, glyoxal, nitrogen dioxide (NO2), water vapor (H2O) and O2-O2 collision complexes (O4/ were measured by the University of Colorado Airborne Multi-AXis Differential Optical Absorption Spectroscopy (CU AMAXDOAS) instrument, aerosol extinction by high spectral resolution lidar (HSRL), in situ aerosol size distributions by an ultra high sensitivity aerosol spectrometer (UHSAS) and in situ H2O by vertical-cavity surface-emitting laser (VCSEL) hygrometer. Data are presented from two research flights (RF12, RF17) aboard the National Science Foundation/ National Center for Atmospheric Research Gulfstream V aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project (January/February 2012). We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols. Our O4-inferred aerosol extinction profiles at 477 nm agree within 6% with HSRL in the boundary layer and closely resemble the renormalized profile shape of Mie calculations constrained by UHSAS at low (sub-Rayleigh) aerosol extinction in the free troposphere. CU AMAX-DOAS provides a flexible choice of geometry, which we exploit to minimize the SCD in the reference spectrum (SCDREF, maximize signal-to-noise ratio) and to test the robustness of BrO, IO and glyoxal differential SCDs. The RF12 case study was conducted in pristine marine and free tropospheric air. The RF17 case study was conducted above the NOAA RV Ka'imimoana (TORERO cruise, KA-12-01) and provides independent validation data from ship-based in situ cavity-enhanced DOAS and MAX-DOAS. Inside the marine boundary layer (MBL) no BrO was detected (smaller than 0.5 pptv), and 0.2-0.55 pptv IO and 32-36 pptv glyoxal were observed. The near-surface concentrations agree within 30% (IO) and 10% (glyoxal) between ship and air-craft. The BrO concentration strongly increased with altitude to 3.0 pptv at 14.5 km (RF12, 9.1 to 8.6 deg N; 101.2 to 97.4 deg W). At 14.5 km, 5-10 pptv NO2 agree with model predictions and demonstrate good control over separating tropospheric from stratospheric absorbers (NO2 and BrO). Our profile retrievals have 12-20 degrees of freedom (DoF) and up to 500m vertical resolution. The tropospheric BrO vertical column density (VCD) was 1.5 x 10(exp 13) molec cm(exp -2) (RF12) and at least 0.5 x 10(exp 13) molec cm(exp -2) (RF17, 0- 10 km, lower limit). Tropospheric IO VCDs correspond to 2.1 x 10(exp 12) molec cm(exp -2) (RF12) and 2.5 x 10(exp 12) molec cm(exp -2) (RF17) and glyoxal VCDs of 2.6 x 10(exp 14) molec cm(exp -2) (RF12) and 2.7 x 10(exp 14) molec cm(exp -2) (RF17). Surprisingly, essentially all BrO as well as the dominant IO and glyoxal VCD fraction was located above 2 km (IO: 58 plus or minus 5 %, 0.1-0.2 pptv; glyoxal: 52 plus or minus 5 %, 3-20 pptv). To our knowledge there are no previous vertically resolved measurements of BrO and glyoxal from aircraft in the tropical free troposphere. The atmospheric implications are briefly discussed. Future studies are necessary to better understand the sources and impacts of free tropospheric halogens and oxygenated hydrocarbons on tropospheric ozone, aerosols, mercury oxidation and the oxidation capacity of the atmosphere.