Southern Hemispheric nitrous oxide measurements obtained during 1987 airborne Antarctic ozone experiment

The chemical lifetime of N2O is about 150 years, which makes it an excellent dynamical tracer of air motion on the time scale of the ozone depletion event. For these reasons it was chosen to help test whether dynamical theories of ozone loss over Antarctica were plausible, particularly the theory that upwelling ozone-poor air from the troposphere was replacing ozone-rich stratospheric air. The N2O measurements were made with the Airborne Tunable Laser Absorption Spectrometer (ATLAS) aboard the NASA ER-2 aircraft. The detection technique involves measuring the diffential absorption of the IR laser radiation as it is rapidly scanned over an N2O absorption feature. For the AAOE mission, the instrument was capable of making measurements with a 1 ppb sensitivity, 1 second response time, over an altitude range of 10 to 20 kilometers. The AAOE mission consisted of a series of 12 flights from Punta Arenas (53S) into the polar vortex (approximately 72S) at which time a vertical profile from 65 to 45 km and back was performed. Comparison of the observed profiles inside the vortex with N2O profiles obtained by balloon flights during the austral summer showed that an overall subsidence had occurred during the winter of about 5 to 6 km. Also, over the course of the mission (mid-August to late September), no trend in the N2O vertical profile, either upward or downward, was discernible, eliminating the possibility that upwelling was the cause of the observed ozone decrease

Small scale structure and mixing at the edge of the Antarctic vortex

Small scale correlations and patterns in the chemical tracers measured from the NASA ER-2 aircraft in the 1987 AAOE campaign can be used to investigate the structure of the edge of the polar vortex and the chemically perturbed region within it. Examples of several types of transport processes can be found in the data. Since ClO and O3 have similar vertical gradients and opposite horizontal gradients near the chemically perturbed region, the correlation between ClO and O3 can be used to study the extent of horizontal transport at the edge of the chemically perturbed region. Horizontal transport dominates the correlation for a latitude band up to 4 degrees on each side of the boundary. This implies a transition zone containing a substantial fraction of the mass of the total polar vortex. Similar horizontal transport can be seen in other tracers as well. It has not been possible to distinguish reversible transport from irreversible mixing. One manifestation of the horizontal transport is that the edge of the chemically perturbed region is often layered rather than a vertical curtain. This can be seen from the frequent reversed vertical gradients of NO2, caused by air with high NO2 overlapping layers with lower mixing ratios. Water and NO2 are positively correlated within the chemically perturbed region. This is the opposite sign to the correlation in the unperturbed stratosphere. The extent of the positive correlation is too great to be attributed solely to horizontal mixing. Instead, it is hypothesized that dehydration and descent are closely connected on a small scale, possibly due to radiative cooling of the clouds that also cause ice to fall to lower altitudes

Correlation of N2O and ozone in the Southern Polar vortex during the airborne Antarctic ozone experiment

In situ N20 mixing ratios, measured by an airborne laser spectrometer (ATLAS), have been used along with in situ ozone measurements to determine the correlation of N2O and ozone in the Antarctic stratosphere during the late austral winter. During the 1987 Airborne Antarctic Ozone Experiment (AAOE), N2O data were collected by a laser absorption spectrometer on board the ER-2 on five ferry flights between Ames Research Center (37 deg N) and Punta Arenas, Chile (53 deg S), and on twelve flights over Antarctica (53 S to 72 S). Of all the trace gas species measured by instruments on board the ER-2, only one showed a relationship to the N2O/O3 correlations in the vortex. With few exceptions, positive N20/O3 correlations coincided with total water mixing ratios of greater than 2.9 ppmv, and total water mixing ratios of less than 2.9 ppmv corresponded to negative correlations. The lower water mixing ratios, or dehydrated regions, are colocated with the negative correlations within the vortex, while the wetter regions always occur near the vortex edge

Temporal trends and transport within and around the Antarctic polar vortex during the formation of the 1987 Antarctic ozone hole

During AAOE in 1987 an ER-2 high altitude aircraft made twelve flights out of Punta Arenas, Chile (53 S, 71 W) into the Antarctic polar vortex. The aircraft was fitted with fast response instruments for in situ measurements of many trace species including O3, ClO, BrO, NO sub y, NO, H2O, and N2O. Grab samples of long-lived tracers were also taken and a scanning microwave radiometer measured temperatures above and below the aircraft. Temperature, pressure, and wind measurements were also made on the flight tracks. Most of these flights were flown to 72 S, at a constant potential temperature, followed by a dip to a lower altitude and again assuming a sometimes different potential temperature for the return leg. The potential temperature chosen was 425 K (17 to 18 km) on 12 of the flight legs, and 5 of the flight legs were flown at 450 K (18 to 19 km). The remaining 7 legs of the 12 flights were not flown on constant potential temperature surfaces. Tracer data have been analyzed for temporal trends. Data from the ascents out of Punta Arenas, the constant potential temperature flight legs, and the dips within the vortex are used to compare tracer values inside and outside the vortex, both with respect to constant potential temperature and constant N2O. The time trend during the one-month period of August 23 through September 22, 1987, shows that ozone decreased by 50 percent or more at altitudes form 15 to 19 km. This trend is evident whether analyzed with respect to constant potential temperature or constant N2O. The trend analysis for ozone outside the vortex shows no downward trend during this period. The analysis for N2O at a constant potential temperature indicates no significant trend either inside or outside the vortex; however, a decrease in N2O with an increase in latitude is evident

The evolution of AAOE observed constituents with the polar vortex

One of the difficulties in determining constituent trends from the ER-2 flight data is the large amount of day to day variability generated by the motion of the polar vortex. To reduce this variability, the observations have been transformed into the conservative (Lagrangian) reference frames consisting of the coordinate pairs, potential temperature (PT) and potential vorticity (PV), or PT and N2O. The requirement of only two independent coordinates rests on the assumption that constituent distributions and their chemical processes are nearly zonal in that coordinate system. Flight data is used everywhere for these transformation except for potential vorticity. Potential vorticity is determined from level flight segments, and NMC PV values during flight dives and takeoffs are combined with flight data in a smooth fashion

Bulk Properties of Isentropic Mixing into the Tropics in the Lower Stratosphere

Timescales for mixing of midlatitude air into the tropical lower stratosphere are deduced from observations of long-lived tracers N2O and CCl3F. Bulk mixing between tropical and midlatitude regions is assumed to be isentropic and relatively slow compared with local mixing within each region. The mean value of the mixing timescale ranges from 12 to 18 months near 20 km. There is a tendency for shorter mixing times at higher and lower altitudes, although vertical profiles of mixing cannot be definitively established by the data. A more robust quantity is given by the fraction of midlatitude air entrained into the tropical upwelling region. Implied mixing fractions exceed 50% above 22 km

Observations of large reductions in the NO/NO_y ratio near the mid-latitude tropopause and the role of heterogeneous chemistry

During the 1993 NASA Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE), anomalously low nitric oxide (NO) was found in a distinct sunlit layer located above the mid-latitude tropopause. The presence of a significant amount of reactive nitrogen (NO_y) in the layer implies the systematic removal of NO, which is without precedent in stratospheric in situ observations. Large increases in measured chlorine monoxide (ClO) and the hydroperoxyl radical (HO_2) also were observed in the layer. Heterogeneous reaction rate constants of chlorine nitrate (ClONO_2) with hydrogen chloride (HCl) and H_2O to form nitric acid (HNO_3) on sulfate aerosol are enhanced in the NO removal layer by local increases in H_2O and aerosol surface area. The associated conversion of NO_x (= NO + NO_2) to HNO_3 is the most likely cause of the observed low NO and NO_x/NO_y values and high ClO values

The response of ClO radical concentrations to variations in NO_2 radical concentrations in the lower stratosphere

The response of ClO concentrations to changes in NO_2 concentrations has been inferred from simultaneous observations of [ClO], [NO], [NO_2] and [O_3] in the mid-latitude lower stratosphere. This analysis demonstrates that [ClO] is inversely correlated with [NO_2], consistent with formation and photolysis of [ClONO_2]. A factor of ten range in the concentration of NO_2 was sampled (0.1 to 1×10^9 mol/cm^3), with a comparable range in the ratio of [ClO] to total available inorganic chlorine (1% ≤ [ClO]/[Cl_y] ≤ 5%). This analysis leads to an estimate of [ClONO_2]/[Cl_y] = 0.12 (×/÷2), in the mid-latitude, lower-stratospheric air masses sampled

Stratospheric NO and NO_2 abundances from ATMOS Solar-Occultation Measurements

Using results from a time-dependent photochemical model to calculate the diurnal variation of NO and NO_2, we have corrected Atmospheric Trace MOlecule Spectroscopy (ATMOS) solar-occultation retrievals of the NO and NO_2 abundances at 90° solar zenith angle. Neglecting to adjust for the rapid variation of these gases across the terminator results in potential errors in retrieved profiles of ∼20% for NO_2 and greater than 100% for NO at altitudes below 25 km. Sensitivity analysis indicates that knowledge of the local O_3 and temperature profiles, rather than zonal mean or climatological conditions of these quantities, is required to obtain reliable retrievals of NO and NO_2 in the lower stratosphere. Extremely inaccurate O_3 or temperature values at 20 km can result in 50% errors in retrieved NO or NO_2. Mixing ratios of NO in the mid-latitude, lower stratosphere measured by ATMOS during the November 1994 ATLAS-3 mission compare favorably with in situ ER-2 observations, providing strong corroboration of the reliability of the adjusted space-borne measurements

Partitioning of the reactive nitrogen reservoir in the lower sratosphere of the southern hemisphere: Observations and modeling

Measurements of nitric oxide (NO), nitrogen dioxide (NO2), and total reactive nitrogen (NOy = NO + NO2 + NO3 + HNO3 + ClONO2 + 2N2O5 + ...) were made during austral fall, winter, and spring 1994 as part of the NASA Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft mission. Comparisons between measured NO2 values and those calculated using a steady state (SS) approximation are presented for flights at mid and high latitudes. The SS results agree with the measurements to within 8%, suggesting that the kinetic rate coefficients and calculated NO2 photolysis rate used in the SS approximation are reasonably accurate for conditions in the lower stratosphere. However, NO2 values observed in the Concorde exhaust plume were significantly less than SS values. Calculated NO2 photolysis rates showed good agreement with values inferred from solar flux measurements, indicating a strong self-consistency in our understanding of UV radiation transmission in the lower stratosphere. Model comparisons using a full diurnal, photochemical steady state model also show good agreement with the NO and NO2 measurements, suggesting that the reactions affecting the partitioning of the NO2 reservoir are well understood in the lower stratosphere