A mechanistic model of photochemical transformation and degradation of colored dissolved organic matter

Abstract

Photochemical degradation (PD) of colored dissolved organic matter (CDOM) is a key transformational process for both natural and anthropogenic DOM. A fully mechanistic model is presented that can simulate laboratory incubations of the controlled PD of marsh and estuarine derived CDOM. The model was designed and optimized to recreate the loss of absorbance for marsh low tide and estuarine samples, representing high molecular weight allochthonous and mid molecular weight estuarine CDOM. In the model, high specific absorbance fractions representative of marsh and estuarine CDOM are transformed into a low specific absorbance fraction representative of coastal ocean CDOM as well as non-colored fractions. The various transformations in the model have maximum apparent quantum yields (at 284 nm) that range from 3.22 × 10−8 ± 1.75 to 56.05 ± 21.5 [mmol C (mol photons)−1], with non-colored DOM/inorganic carbon production outpaced by inter-molecular organic carbon transformations. Model performance was tested using an independent incubation data set whereby experimental results of photobleaching of spectral absorbance at 300 nm were recreated with a Willmott model skill of 0.98 and mean percent error of −3.66%. The production of the low molecular weight photodegraded end member ranged from 0.52 to 4.86 μmol C L−1 h−1.