ALBERT

Description: Eleven particle samples collected in the polar stratosphere during SOLVE (SAGE III Ozone loss and validation experiment) from January until March 2000 were characterized in detail by high-resolution transmission and scanning electron microscopy (TEM/SEM) combined with energy-dispersive X-ray microanalysis. A total of 4202 particles (TEM  =  3872; SEM  =  330) were analyzed from these samples, which were collected mostly inside the polar vortex in the altitude range between 17.3 and 19.9 km. Particles that were volatile in the microscope beams contained ammonium sulfates and hydrogen sulfates and dominated the samples. Some particles with diameters ranging from 20 to 830 nm were refractory in the electron beams. Carbonaceous particles containing additional elements to C and O comprised from 72 to 100 % of the refractory particles. The rest were internal mixtures of these materials with sulfates. The median number mixing ratio of the refractory particles, expressed in units of particles per milligram of air, was 1.1 (mg air)−1 and varied between 0.65 and 2.3 (mg air)−1. Most of the refractory carbonaceous particles are completely amorphous, a few of the particles are partly ordered with a graphene sheet separation distance of 0.37 ± 0.06 nm (mean value ± standard deviation). Carbon and oxygen are the only detected major elements with an atomic O∕C ratio of 0.11 ± 0.07. Minor elements observed include Si, S, Fe, Cr and Ni with the following atomic ratios relative to C: Si∕C: 0.010 ± 0.011; S∕C: 0.0007 ± 0.0015; Fe∕C: 0.0052 ± 0.0074; Cr∕C: 0.0012 ± 0.0017; Ni∕C: 0.0006 ± 0.0011 (all mean values ± standard deviation).High-resolution element distribution images reveal that the minor elements are distributed within the carbonaceous matrix; i.e., heterogeneous inclusions are not observed. No difference in size, nanostructure and elemental composition was found between particles collected inside and outside the polar vortex. Based on chemistry and nanostructure, aircraft exhaust, volcanic emissions and biomass burning can certainly be excluded as sources. The same is true for the less probable but globally important sources: wood burning, coal burning, diesel engines and ship emissions. Recondensed organic matter and extraterrestrial particles, potentially originating from ablation and fragmentation, remain as possible sources of the refractory carbonaceous particles studied. However, additional work is required in order to identify the sources unequivocally.

Description: A condensation nucleus counter which operated at stratospheric pressures was developed, designed, and constructed. It was calibrated in the laboratory. Its response as a function of particle size and concentration was reported. This was the first time that the response of such an instrument was verified in the laboratory. An inlet was constructed which provided near isokinetic sampling. The resulting instrument, the U-2 CNC, was deployed on NASA U-2 aircraft in the study of the climatic effects of aerosol. These studies occurred in March, April, May, July, November, and December of 1992 and in April, May, June, and December of 1983. The U-2 CNC was used in the study of the aerosol cloud resulting from the eruption of El Chichon. It permitted the observation of new particle formation in the stratosphere.

Description: The ER-2 condensation nuclei counter (CNC) has been modified to reduce the diffusive losses of particles within the instrument. These changes have been successful in improving the counting efficiency of small particles at low pressures. Two techniques for measuring the size distributions of particles with diameters less than 0.17 micrometers have been evaluated. Both of these methods, the differential mobility analyzer (DMA) and the diffusion battery, have fundamental problems that limit their usefulness for stratospheric applications. We cannot recommend either for this application. Newly developed, alternative methods for measuring small particles include inertial separation with a low-loss critical orifice and thin-plate impactor device. This technique is now used to collect particles in the multisample aerosol collector housed in the ER-2 CNC-2, and shows some promise for particle size measurements when coupled with a CNC as a counting device. The modified focused-cavity aerosol spectrometer (FCAS) can determine the size distribution of particles with ambient diameters as small as about 0.07 micrometers. Data from this instrument indicates the presence of a nuclei mode when CNC-2 indicates high concentrations of particles, but cannot resolve important parameters of the distribution.

Description: There were two principal objectives of the cooperative agreement between NASA and the University of Denver. The first goal was to modify the design of the ER-2 condensation nuclei counter (CNC) so that the effective lower detection limit would be improved at high altitudes. This improvement was sought because, in the instrument used prior to 1993, diffusion losses prevented the smallest detectable particles from reaching the detection volume of the instrument during operation at low pressure. Therefore, in spite of the sensor's ability to detect particles as small as 0.008 microns in diameter, many of these particles were lost in transport to the sensing region and were not counted. Most of the particles emitted by aircraft are smaller than 0.1 micron in diameter. At the start date of this work, May 1990, continuous sizing techniques available on the ER-2 were only capable of detecting particles larger than 0.17 micron. Thus, the second objective of this work was to evaluate candidate sizing techniques in an effort to gain additional information concerning the size of particles emitted by aircraft.

Description: The work done on this grant primarily concerns the measurement of aerosol in the stratosphere from NASA ER-2 aircraft in studies of stratospheric ozone depletion in the northern and southern hemispheres. The ER-2 Condensation Nucleus Counter (CNC) measures the number concentration of particles in the diameter range of approximately 0.01 to 1 micron. The Passive Cavity Aerosol Spectrometer measures size distributions in the 0.17 to 3 micron diameter range. This instrument was upgraded during this grant period to a Focused Cavity Aerosol Spectrometer (FCAS). This upgrade permitted the instrument to measure particles as small as 0.05 micron in diameter. The inlet for the PCAS and FCAS was modified and characterized under this grant so that the modifications to the aerosol due to anisokinetic sampling and heating upon sampling and in transport to the measurement location were accounted for in the data analysis. These measurements permitted observations of particle production in the southern hemisphere winter polar vortex and observation of the impact of denitrification on the number concentration of the aerosol in the denitrified air. In the northern polar vortex, the measurements provided a characterization of the sulfate aerosol. Following the eruption of Mount Pinatubo in 1991, the measurements permitted an accurate characterization of the sulfate aerosol enhancements resulting from the eruption. This led to studies of the impact of heterogeneous chemistry on the partitioning of the partitioning of the reactive nitrogen species and the partitioning of the chlorine reservoir.

Description: The University of Denver Aerosol Group proposed to adapt an impactor system for the collection of particles emitted by aircraft. The collection substrates were electron microscope grids which were analyzed by Dr. Pat Sheridan using a transmission electron microscope. The impactor was flown in the SNIFF behind aircraft and engine emissions were sampled. This report details the results of that work.

Description: The University of Denver agreed to develop and fabricate two instruments for the characterization of submicron aerosol. The instruments were to be light weight for use on remotely-piloted aircraft or balloons. The instruments were to provide accurate size measurements of size distributions in the size range from 0.07 to 2 micrometers in diameter and concentration measurements in the size range approximately 0.01 to 2 micrometers in diameter. The instruments constructed under this cooperative agreement respond quite nearly as expected and meet the objective of being light and compact. One has been used for ground based and low altitude studies and the other will be deployed in high altitude studies this winter.