Photo-tautomerization of acetaldehyde as a photochemical source of formic acid in the troposphere

Organic acids play a key role in the troposphere, contributing to atmospheric aqueous-phase chemistry, aerosol formation, and precipitation acidity. Atmospheric models currently account for less than half the observed, globally averaged formic acid loading. Here we report that acetaldehyde photo-tautomerizes to vinyl alcohol under atmospherically relevant pressures of nitrogen, in the actinic wavelength range, λ = 300–330 nm, with measured quantum yields of 2–25%. Recent theoretical kinetics studies show hydroxyl-initiated oxidation of vinyl alcohol produces formic acid. Adding these pathways to an atmospheric chemistry box model (Master Chemical Mechanism) demonstrates increased formic acid concentrations by a factor of ~1.7 in the polluted troposphere and a factor of ~3 under pristine conditions. Incorporating this mechanism into the GEOS-Chem 3D global chemical transport model reveals an estimated 7% contribution to worldwide formic acid production, with up to 60% of the total modeled formic acid production over oceans arising from photo-tautomerization

Forward model and Jacobians for Tropospheric Emission Spectrometer retrievals

The Tropospheric Emission Spectrometer (TES) is a high-resolution spaceborne sensor that is capable of observing tropospheric species. In order to exploit fully TES's potential for tropospheric constituent retrievals, an accurate and fast operational forward model was developed for TES. The forward model is an important component of the TES retrieval model, the Earth Limb and Nadir Operational Retrieval (ELANOR), as it governs the accuracy and speed of the calculations for the retrievals. In order to achieve the necessary accuracy and computational efficiency, TES adopted the strategy of utilizing precalculated absorption coefficients generated by the line-by-line calculations provided by line-by-line radiation transfer modeling. The decision to perform the radiative transfer with the highest monochromatic accuracy attainable, rather than with an accelerated scheme that has the potential to add algorithmic forward model error, has proven to be very successful for TES retrievals. A detailed description of the TES forward model and Jacobians is described. A preliminary TES observation is provided as an example to demonstrate that the TES forward model calculations represent TES observations. Also presented is a validation example, which is part of the extensive forward model validation effort. © 2006 IEEE