Photochemical Implications of Changes in the Spectral Properties of Chromophoric Dissolved Organic Matter: A Model Assessment for Surface Waters

Chromophoric dissolved organic matter (CDOM) is the main sunlight absorber in surface waters and a very important photosensitiser towards the generation of photochemically produced reactive intermediates (PPRIs), which take part in pollutant degradation. The absorption spectrum of CDOM (A(CDOM)(λ), unitless) can be described by an exponential function that decays with increasing wavelength: A(CDOM)(λ) = 100 d DOC A(o) e(−) (S) (λ), where d [m] is water depth, DOC [mg(C) L(−1)] is dissolved organic carbon, A(o) [L mg(C)(−1) cm(−1)] is a pre-exponential factor, and S [nm(−1)] is the spectral slope. Sunlight absorption by CDOM is higher when A(o) and DOC are higher and S is lower, and vice versa. By the use of models, here we investigate the impact of changes in CDOM spectral parameters (A(o) and S) on the steady-state concentrations of three PPRIs: the hydroxyl radical ((•)OH), the carbonate radical (CO(3)(•−)), and CDOM excited triplet states ((3)CDOM*). A first finding is that variations in both A(o) and S have impacts comparable to DOC variations on the photochemistry of CDOM, when reasonable parameter values are considered. Therefore, natural variability of the spectral parameters or their modifications cannot be neglected. In the natural environment, spectral parameters could, for instance, change because of photobleaching (prolonged exposure of CDOM to sunlight, which decreases A(o) and increases S) or of the complex and still poorly predictable effects of climate change. A second finding is that, while the steady-state [(3)CDOM*] would increase with increasing A(CDOM) (increasing A(o), decreasing S), the effect of spectral parameters on [(•)OH] and [CO(3)(•−)] depends on the relative roles of CDOM vs. NO(3)(−) and NO(2)(−) as photochemical (•)OH sources.