Thermochromism of Model Organic Aerosol Matter

Abstract

Laboratory experiments show that the optical absorptivity of model organic matter is not an intrinsic property, but a strong function of relative humidity, temperature, and insolation. Suites of representative polyfunctional CxHyOz oligomers in water develop intense visible absorptions upon addition of inert electrolytes. The resulting mixtures reach mass absorption cross sections σ(532 nm) ∼ 0.1 m2/gC in a few hours, absorb up to 9 times more solar radiation than the starting material, can be half-bleached by noon sunlight in ∼1 h, and can be repeatedly recycled without carbon loss. Visible absorptions red-shift and evolve increasingly faster in subsequent thermal aging cycles. Thermochromism and its strong direct dependences on ionic strength and temperature are ascribed to the dehydration of >CH−C(OH)< groups into >C═C< unsaturations by a polar E1 mechanism, and bleaching to photoinduced retrohydration. These transformations are deemed to underlie the daily cycles of aerosol absorption observed in the field, and may introduce a key feedback in the earth’s radiative balance.