Abstract. Accurate mean ages for stratospheric air have been derived from a spatially and temporally comprehensive set of in situ observations of CO2, CH4, and N20 obtained from 1992 to 1998 from the NASA ER-2 aircraft and balloon flights. Errors associated with the tropospheric CO2 seasonal cycle and interannual variations in the CO2 growth rate are ( 0.5 year throughout the stratosphere and ( 0.3 year for air older than 2 years (N20 < 275 ppbv), indicating that the age spectra are broad enough to attenuate these influences over the time period covered by these observations. The distribution of mean age with latitude and altitude provides detailed, quantitative information about the general circulation of the stratosphere. At 20 km, sharp meridional gradients in the mean age are observed across the subtropics. Between 20 and 30 km, the average difference in mean age between the tropics and midlatitudes is -2 years, with slightly smaller differences at higher and lower altitudes. The mean age in the midlatitude middle stratosphere (-25-32 km) is relatively constant with respect to altitude at 5 _ 0.5 years. Comparison with earlier balloon observations of CO2 dating back to the 1970s indicates that the mean age of air in this region has remained within _+1 year of its current value over the last 25 years. A climatology of mean age is derived from the observed compact relationship between mean age and N20. These characteristics of the distribution of mean age in the stratosphere will serve as critically needed diagnostics for models of stratospheric transport.

Abstract. 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 AMAX-DOAS) 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 aircraft. The BrO concentration strongly increased with altitude to 3.0 pptv at 14.5 km (RF12, 9.1 to 8.6° N; 101.2 to 97.4° 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 500 m vertical resolution. The tropospheric BrO vertical column density (VCD) was 1.5 × 1013 molec cm−2 (RF12) and at least 0.5 × 1013 molec cm−2 (RF17, 0–10 km, lower limit). Tropospheric IO VCDs correspond to 2.1 × 1012 molec cm−2 (RF12) and 2.5 × 1012 molec cm−2 (RF17) and glyoxal VCDs of 2.6 × 1014 molec cm−2 (RF12) and 2.7 × 1014 molec cm−2 (RF17). Surprisingly, essentially all BrO as well as the dominant IO and glyoxal VCD fraction was located above 2 km (IO: 58 ± 5%, 0.1–0.2 pptv; glyoxal: 52 ± 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.

Halogens in the troposphere are increasingly recognized as playing an important role for atmospheric chemistry, and possibly climate. Bromine and iodine react catalytically to destroy ozone (O 3 ), oxidize mercury, and modify oxidative capacity that is relevant for the lifetime of greenhouse gases. Most of the tropospheric O 3 and methane (CH 4 ) loss occurs at tropical latitudes. Here we report simultaneous measurements of vertical profiles of bromine oxide (BrO) and iodine oxide (IO) in the tropical and subtropical free troposphere (10°N to 40°S), and show that these halogens are responsible for 34% of the column-integrated loss of tropospheric O 3 . The observed BrO concentrations increase strongly with altitude (∼3.4 pptv at 13.5 km), and are 2-4 times higher than predicted in the tropical free troposphere. BrO resembles model predictions more closely in stratospheric air. The largest model low bias is observed in the lower tropical transition layer (TTL) over the tropical eastern Pacific Ocean, and may reflect a missing inorganic bromine source supplying an additional 2.5-6.4 pptv total inorganic bromine (Br y ), or model overestimated Br y wet scavenging. Our results highlight the importance of heterogeneous chemistry on ice clouds, and imply an additional Br y source from the debromination of sea salt residue in the lower TTL. The observed levels of bromine oxidize mercury up to 3.5 times faster than models predict, possibly increasing mercury deposition to the ocean. The halogen-catalyzed loss of tropospheric O 3 needs to be considered when estimating past and future ozone radiative effects.atmospheric chemistry | oxidative capacity | halogens | heterogeneous chemistry | UTLS T ropospheric halogens catalytically destroy O 3 (1−3), oxidize atmospheric mercury (4, 5), and modify the oxidative capacity of the atmosphere (6). O 3 is a potent greenhouse gas (7), and an important precursor for hydroxyl (OH) radicals (6, 8) that determine the lifetime of CH 4 another important greenhouse gas. About 75% of the global tropospheric O 3 (3) and CH 4 (8) loss occurs at tropical latitudes, where O 3 radiative forcing is also most sensitive to changes in O 3 (9). Halogen chemistry is thought responsible for ∼10% of the tropical tropospheric O 3 column loss (3), yet atmospheric models remain essentially untested due to the lack of vertically resolved halogen radical measurements in the tropical troposphere. Column observations from ground and satellites (10−18), including measurements in the tropics (14, 16−18), point to the existence of a-possibly ubiquitous-tropospheric BrO background concentration of ∼1−2 parts per trillion by volume (pptv) that currently remains unexplained by models, and would be of significant relevance for O 3 , OH, and mercury oxidation (2−6, 8). Recently, corroborating evidence is emerging from a measurement in the tropical free troposphere (FT) (19). IO has been detected in the Northern Hemisphere (NH) FT (19−21), but there is currently no vertically resolved measurement of BrO or IO in the ...

[1] The amount of chlorine in the stratosphere has a direct influence on the magnitude of chlorine-catalyzed ozone loss. A comprehensive suite of organic source gases of chlorine in the stratosphere was measured during the NASA Stratospheric Aerosol and Gas Experiment (SAGE) III Ozone Loss and Validation Experiment (SOLVE) campaign in the arctic winter of 2000. Measurements included chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), halon 1211, solvents, methyl chloride, N 2 O, and CH 4 . Inorganic chlorine contributions from each compound were calculated using the organic chlorine measurements, mean age of air, tropospheric trends, and a method to account for mixing in the stratosphere. Total organic chlorine measured at tropospheric levels of N 2 O was on the order of 3500 ppt. Total calculated inorganic chlorine at a N 2 O mixing ratio of 50 ppb (corresponding to a mean age of 5.5 years) was on the order of 3400 ppt. CFCs were the largest contributors to total organic chlorine (55-70%) over the measured N 2 O range (50-315 ppb), followed by CH 3 Cl (15%), solvents (5-20%), and HCFCs (5-25%). CH 3 Cl contribution was consistently about 15% across the organic chlorine range. Contributions to total calculated inorganic chlorine at 50 ppb N 2 O were 58% from CFCs, 24% from solvents, 16% from CH 3 Cl, and 2% from HCFCs. Updates to fractional chlorine release values for each compound relative to CFC 11 were calculated from the SOLVE measurements. An average value of 0.58 was calculated for the fractional chlorine release of CFC 11 over the 3-4 year mean age range, which was lower than the previous value of 0.80. The fractional chlorine release values for HCFCs 141b and 142b relative to CFC 11 were significantly lower than previous calculations.

During the Deep Propagating Gravity Wave Experiment (DEEPWAVE) project in June and July 2014, the Gulfstream V research aircraft flew 97 legs over the Southern Alps of New Zealand and 150 legs over the Tasman Sea and Southern Ocean, mostly in the low stratosphere at 12.1-km altitude. Improved instrument calibration, redundant sensors, longer flight legs, energy flux estimation, and scale analysis revealed several new gravity wave properties. Over the sea, flight-level wave fluxes mostly fell below the detection threshold. Over terrain, disturbances had characteristic mountain wave attributes of positive vertical energy flux (EF z ), negative zonal momentum flux, and upwind horizontal energy flux. In some cases, the fluxes changed rapidly within an 8-h flight, even though environmental conditions were nearly unchanged. The largest observed zonal momentum and vertical energy fluxes were MF x 5 2550 mPa and EF z 5 22 W m 22 , respectively. A wide variety of disturbance scales were found at flight level over New Zealand. The vertical wind variance at flight level was dominated by short ''fluxless'' waves with wavelengths in the 6-15-km range. Even shorter scales, down to 500 m, were found in wave breaking regions. The wavelength of the flux-carrying mountain waves was much longer-mostly between 60 and 150 km. In the strong cases, however, with EF z . 4 W m 22, the dominant flux wavelength decreased (i.e., ''downshifted'') to an intermediate wavelength between 20 and 60 km. A potential explanation for the rapid flux changes and the scale ''downshifting'' is that low-level flow can shift between ''terrain following'' and ''envelope following'' associated with trapped air in steep New Zealand valleys.