The occurrence of pristine and functionalized fullerenes as constituents of airborne aerosols

We investigated if pristine and functionalized fullerenes could be actual constituents of fine atmospheric aerosols. Comprehensive profiles of fullerenes from 1 µL extracts were made through matrix laser desorption ionization Time-of-Flight Mass Spectrometry (MALDI-MS) within a few minutes. The ion with m/z 720, corresponding to [C₆₀]^-•, was identified as fullerene after 1 µL of α-cyano-4-hydroxycinnamic acid matrix solution was spotted over the dried extracts. The ions with the m/z corresponding to C₇₀, C₇₆, C₈₄, C₁₀₀, C₁₁₈, C₁₂₈, and C₁₃₀ were also attributed to other fullerene species detected within the samples. The ion m/z 878 was found to be the fullerene derivative diethyl methano[60]fullerene dicarboxylate. Since ions of fragmented fullerene molecules were not detected even at high laser energies, we considered the fullerenes' occurring as original constituents of real atmospheric particle matrices instead of being formed as artifacts of the laser action on samples. Therefore, this protocol would be helpful in the understanding of the distribution of either pristine or functionalized fullerenes in the environment and their participation in atmospheric chemistry under typical conditions, as well as its application in vitro and in vivo (eco)toxicity studies.