Absorption and fluorescence properties of rainwater during the cold season at a town in Western Portugal

This study aims at evaluating the variability of the optical properties of chromophoric dissolved organic matter (CDOM) of rainwater during the cold season, specifically between Autumn and Winter periods. The spectroscopic characteristics of rainwater samples collected at a town (Aveiro) in western Portugal were assessed by UV-Vis absorbance and three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopies. Rainwater samples showed similar characteristics to those of natural humic substances when analysed by UV-Vis absorbance spectroscopy, but a significant difference was observed in the volume weight average (VWA) of absorbances between Autumn and Winter. In general, the EEM fluorescence spectra of the Autumn and Winter samples disclosed the presence of six fluorophores with different VWA specific fluorescence intensities: three humic-like (λ _excitation/λ _emission ≈ 230/415 nm; 290/415 nm; and 340/415 nm) and three protein-like (λ _excitation/λ _emission ≈ 230/350 nm; 280/340 nm; and 225/300 nm), but one of the humic-like peaks (≈340/415 nm) does not always appear in the EEM fluorescence spectra of the Winter samples. During the cold season, chromophoric compounds are important constituents of rainwater dissolved organic matter and the presence of these highly absorbing and fluorescing compounds may exert a determining effect in atmospheric absorption of solar radiation.