Uptake of acetone,acetaldehyde and ethanol in cold sulfuric acid solutions containing organic material: Carbon accretion mechanisms

The solubilities of acetone, ethanol and acetaldehyde in cold ternary solutions composed of 38.4–75.0 wt% sulfuric acid in water with additional dissolved organic material have been measured over the temperature range 214.4–238.5 K using a Knudsen cell reactor. The solubility of acetaldehyde in H₂SO₄/H₂O is enhanced by an order of magnitude by the presence of ethanol or acetone. The reactive uptake of acetaldehyde is enhanced by the presence of formaldehyde in acid solution. No significant formation of acetals from ethanol with carbonyl partners was observed. The solubility of acetone is unaffected by the presence of ethanol in solution and vice versa. Only polymerization of small aldehydes offers a potentially significant route to the accretion of organic material into acidic particles in the upper troposphere. The acid-catalyzed polymerization of aldehydes, RC(H)O + R′C(H)O, proceeds through the hydrated forms of the aldehydes, is optimized at acidities around 40 wt% H₂SO₄, and can potentially accumulate significant amounts (>20%) of organic material by mass in upper tropospheric particles.