The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3 in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HOx required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of O3 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day. This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more O3 than expected.

We observed a plume of air highly enriched in carbon monoxide and particles in the stratosphere at altitudes up to 15.8 km. It can be unambiguously attributed to North American forest fires. This plume demonstrates an extra‐tropical direct transport path from the planetary boundary layer several kilometers deep into the stratosphere, which is not fully captured by large‐scale atmospheric transport models. This process indicates that the stratospheric ozone layer could be sensitive to changes in forest burning associated with climatic warming.

Optically thin cirrus near the tropical tropopause regulate the humidity of air entering the stratosphere, which in turn has a strong influence on the Earth's radiation budget and climate. Recent highaltitude, unmanned aircraft measurements provide evidence for two distinct classes of cirrus formed in the tropical tropopause region: (i) vertically extensive cirrus with low ice number concentrations, low extinctions, and large supersaturations (up to ∼70%) with respect to ice; and (ii) vertically thin cirrus layers with much higher ice concentrations that effectively deplete the vapor in excess of saturation. The persistent supersaturation in the former class of cirrus is consistent with the long time-scales (several hours or longer) for quenching of vapor in excess of saturation given the low ice concentrations and cold tropical tropopause temperatures. The low-concentration clouds are likely formed on a background population of insoluble particles with concentrations less than 100 L −1 (often less than 20 L −1 ), whereas the high ice concentration layers (with concentrations up to 10,000 L −1 ) can only be produced by homogeneous freezing of an abundant population of aqueous aerosols. These measurements, along with past high-altitude aircraft measurements, indicate that the low-concentration cirrus occur frequently in the tropical tropopause region, whereas the high-concentration cirrus occur infrequently. The predominance of the low-concentration clouds means cirrus near the tropical tropopause may typically allow entry of air into the stratosphere with as much as ∼1.7 times the ice saturation mixing ratio. ATTREX | ice nucleiA lthough the stratosphere is extremely dry compared with the troposphere, stratospheric humidity plays crucial roles in both atmospheric chemistry and climate. As the primary source of hydroxyl (OH) radicals, H 2 O plays an important role in the regulation of stratospheric ozone. Small changes in stratospheric humidity can have significant influence on the Earth's radiation budget and climate (1, 2). Model simulations show that increases in stratospheric humidity enhance the rate of ozone destruction, cool the lower stratosphere, and warm the surface (3, 4).Air enters the stratospheric overworld (above 380 K potential temperature) almost exclusively via ascent across the tropical tropopause. This fact has motivated interest in understanding processes occurring in the transition layer between the tropical troposphere and stratosphere, a region of the atmosphere referred to as the Tropical Tropopause Layer (TTL). Physical processes occurring in this layer set the boundary condition for the composition and humidity of the stratosphere. It is well established that the aridity of the stratosphere is associated with "freeze-drying" of air as it passes through the cold TTL (5, 6). Deposition growth of ice crystals in optically thin, laminar TTL cirrus depletes vapor in excess of saturation, and the ice crystals sediment relative to the slowly ascending air. The common occurrence of these thin, ...