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RESEARCH PRODUCT

Sub 500 nm refractory carbonaceous particles in the polar stratosphere

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Abstract. 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 number of 4175 particles (TEM = 3845; SEM = 330) was analyzed from these samples which were collected mostly inside the polar vortex in the altitude range between 17.3 and 19.9 km. By particle volume, all samples are dominated by volatile particles (ammonium sulfates/hydrogen sulfates). By number, approximately 28–82 % of the particles are refractory carbonaceous with sizes between 20–830 nm. Internal mixtures of refractory carbonaceous and volatile particles comprise up to 16 %, individual volatile particles about 9 to 72 %. 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 source. The same is true for the less probable, but globally important sources: wood burning, coal burning, diesel engines and ship emissions. Rocket exhaust and carbonaceous material from interplanetary dust particles remain as possible sources of the refractory carbonaceous particles studied. However, additional work is required in order to identify the sources unequivocally.