Abstract. Biogenic isoprene fluxes were measured onboard the CIRPAS Twin Otter aircraft as part of the California Airborne Biogenic volatile organic compound (BVOC) Emission Research in Natural Ecosystem Transects (CABERNET) campaign during June 2011. The airborne virtual disjunct eddy covariance (AvDEC) approach used measurements from a proton transfer reaction mass spectrometer (PTR–MS) and a wind radome probe to directly determine fluxes of isoprene over 7400 km of flight paths focusing on areas of California predicted to have the largest emissions. The fast Fourier transform (FFT) approach was used to calculate fluxes of isoprene over long transects of more than 15 km, most commonly between 50 and 150 km. The continuous wavelet transformation (CWT) approach was used over the same transects to also calculate instantaneous isoprene fluxes with localization of both frequency and time independent of non-stationarities. Fluxes were generally measured by flying consistently at 400 m ± 50 m (a.g.l.) altitude, and extrapolated to the surface according to the determined flux divergence determined in the racetrack-stacked profiles. The wavelet-derived surface fluxes of isoprene averaged to 2 km spatial resolution showed good correspondence to basal emission factor (BEF) land-cover data sets used to drive BVOC emission models. The surface flux of isoprene was close to zero over Central Valley crops and desert shrublands, but was very high (up to 15 mg m−2 h−1) above oak woodlands, with clear dependence of emissions on temperature and oak density. Isoprene concentrations of up to 8 ppb were observed at aircraft height on the hottest days and over the dominant source regions. Even though the isoprene emissions from agricultural crop regions, shrublands, and coniferous forests were extremely low, observations at the Walnut Grove tower south of Sacramento demonstrate that isoprene oxidation products from the high emitting regions in the surrounding oak woodlands accumulate at night in the residual layer above the valley and mix down into the valley in the morning. Thus, the isoprene emissions surrounding the valley have relevance for the regional photochemistry that is not immediately apparent solely from the direct emission flux distribution. This paper reports the first regional observations of fluxes from specific sources by eddy covariance from an aircraft which can finally constrain statewide isoprene emission inventories used for ozone simulations by state agencies. While previously there was no available means to constrain the biogenic models, our results provide a good understanding of what the major sources of isoprene are in California, their magnitude, and how they are distributed. This data set on isoprene fluxes will be particularly useful for evaluating potential model alternatives which will be dealt with in a separate paper to assess isoprene emission models and their driving variable data sets.

Highly resolved aerosol size distributions measured from high-altitude aircraft can be used to describe the effect of the 1991 eruption of Mount Pinatubo on the stratospheric aerosol. In some air masses, aerosol mass mixing ratios increased by factors exceeding 100 and aerosol surface area concentrations increased by factors of 30 or more. Increases in aerosol surface area concentration were accompanied by increases in chlorine monoxide at mid-latitudes when confounding factors were controlled. This observation supports the assertion that reactions occurring on the aerosol can increase the fraction of stratospheric chlorine that occurs in ozone-destroying forms.

In situ measurements of hydrogen, nitrogen, and chlorine radicals obtained in the lower stratosphere during SPADE are compared to results from a photochemical model that assimilates measurements of radical precursors and environmental conditions. Models allowing for heterogeneous hydrolysis of N205 agree well with measured concentrations of NO and C10, but concentrations of HO2 and OH are underestimated by 10 to 25%, concentrations of NO 2 are overestimated by 10 to 30%, and concentrations of HC1 are overestimated by a factor of 2. Discrepancies for [OH] and [HO2] are reduced if we allow for higher yields of O( 1 D) from O3 photolysis and for heterogeneousproduction of HNO:. The data suggest more efficient catalytic removal of O3 by hydrogen and halogen radicals relative to nitrogen oxide radicals than predicted by models using recommended rates and cross sections. Increases in [03] in the lower stratosphere may be larger in response to inputs of NO• from supersonic aircraft than estimated by current assessment models.

Abstract. Measurements of aerosol, N 2 O and OCS made in the Northern Hemisphere below 21 km altitude following the eruption of Pinatubo are presented and analyzed. After September 1999, the oxidation of OCS and sedimentation of particles in the extra-tropical overworld north of 45 N are found to maintain the aerosol in a steady state. This analysis empirically links precursor gas to aerosol abundance throughout this region. These processes are tracked with ageof-air which offers advantages over tracking as a function of latitude and altitude. In the extra-tropical, lowermost stratosphere, normalized volume distributions appear constant in time after the fall of 1999. Exchange with the troposphere is important in understanding aerosol evolution there. Size distributions of volcanically perturbed aerosol are included to distinguish between volcanic and non-volcanic conditions. This analysis suggests that model failures to correctly predict OCS and aerosol properties below 20 km in the Northern Hemisphere extra tropics result from inadequate descriptions of atmospheric circulation.

No abstract

In situ measurements of NO and NOy are used to derive the ratio NOx/NOy along the flight track of the NASA ER‐2 aircraft. Data are presented for two flights at mid‐latitudes in October 1991 during the Airborne Arctic Stratospheric Expedition‐II (AASE‐II). Aerosol particle surface area was concurrently measured. The observations are compared with a photochemical model integrated along back trajectories from the aircraft flight track. Comparison of observations with the model run along trajectories and at a fixed position clearly and quantitatively demonstrates the importance of an air parcel's dynamic history in interpretation of local chemical observations. Comparison of the data with model runs under different assumptions regarding heterogeneous chemistry further reinforces the case for occurrence of the reaction of N2O5 + H2O on sulfate aerosol surfaces in the atmosphere. Finally, comparisons for which relative changes in the model and the data are not consistent caution that our ability to resolve all the observations is not yet complete.

Two optical particle counters on the ER‐2, together covering a particle size diameter range from 0.1 μm to 23 μm, were used to measure the aerosol bulk quantities integral number, aerosol surface and volume, as well as detailed size distributions inside and outside of the polar vortex in the lower stratosphere. While AASE I (Arctic Airborne Stratospheric Expedition, (Dec. 88‐Feb. 89) was conducted in a period of relative volcanic quiescence, enhancements in aerosol number, surface and volume of factors around 10, 25 and 100 were observed during AASE II (Aug. 91‐Mar. 92) due to the eruption of Mt. Pinatubo. The changes in these bulk quantities as well as in the size distributions measured both outside and inside the the polar vortex are presented and compared with those obtained in polar stratospheric cloud events (AASE I). Except for a shift towards larger aerosol mixing ratios the general shape of correlograms between the measured N2O and particle mixing ratios remain similar before and after the eruption. Similar correlograms are used to interpret data from vertical profiles inside and outside of the polar vortex.

Since the eruption of Mount Pinatubo in June, 1991, measurements of particle size and concentration have intermittently been carried out from an ER‐2 aircraft at altitudes of up to 21 km at midlatitudes and high latitudes in the northern hemisphere. They show the evolution and purge of the volcanic aerosol to be due to an interaction of aerosol mechanics with tropospheric‐stratospheric exchange processes, transport, and mixing. During the first 5 months after the eruption the volcanic plume spread to higher latitudes in laminae and filaments, producing steep spatial gradients in the properties of the stratospheric aerosol. At the same time the concentration of newly formed particles in the plume rapidly decreased toward background values as a result of coagulation while particle size and aerosol surface area continued to increase. By December 1991, the particle number mixing ratios and aerosol surface area mixing ratios had become spatially uniform over a wide range of latitudes above 18 km. The surface area mixing ratios peaked in this region of the stratosphere at ∼35 times their background values in the winter of 1992. The corresponding condensed mass mixing ratio enhancement was by a factor of ∼200. After the winter of 1992, a gradual removal of the volcanic mass began and initially was dominated by sedimentation above 18 km. The aerosol surface area mixing ratio thus decreased by an order of magnitude over 2.5 years, and the aerosol volume, or condensed mass, mixing ratio decayed by an order of magnitude over approximately 1.7 years. Below 18 km, the purging of the Pinatubo aerosol at mid‐latitudes appeared sporadic and disorderly and was strongly influenced by episodal rapid quasi‐isentropic transport and dilution by tropical air of tropospheric origin having high condensation nuclei mixing ratios but low mixing ratios of aerosol surface area or condensed mass compared to the volcanic aerosol.