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. Glyoxal (CHOCHO) and methylglyoxal (CH3C(O)CHO) are well-known components of atmospheric particles and their properties can impact atmospheric chemistry and cloud formation. To get information on their hydration states in aqueous solutions and how they are affected by the addition of inorganic salts (sodium chloride (NaCl) and sodium sulfate (Na2SO4)), we applied carbon and oxygen K-edge X-ray absorption spectroscopy (XAS) in transmission mode. The recorded C K-edge spectra show that glyoxal is completely hydrated in the dilute aqueous solutions, in line with previous studies. For methylglyoxal, supported by quantum chemical calculations we identified not only C–H, C=O and C–OH bonds, but also fingerprints of C–OH(CH2) and C=C bonds. The relatively low intensity of C=O transitions implies that the monohydrated form of methylglyoxal is not favored in the solutions. Instead, the spectral intensity is stronger in regions where products of aldol condensation and enol tautomers of the monohydrates contribute. The addition of salts was found to introduce only very minor changes to absorption energies and relative intensities of the observed absorption features, indicating that XAS in the near-edge region is not very sensitive to these intermolecular organic–inorganic interactions at the studied concentrations. The identified structures of glyoxal and methylglyoxal in an aqueous environment support the uptake of these compounds to the aerosol phase in the presence of water and their contribution to secondary organic aerosol formation.

Aqueous-phase behavior of glyoxal and methylglyoxal observed with carbon and oxygen K-edge X-ray absorption spectroscopy