Insights on Dissolved Organic Matter Production Revealed by Removal of Charge-Transfer Interactions in Senescent Leaf Leachates

Dissolved organic matter (DOM) is a critical part of the global carbon cycle. Currently, it is understood that at least a portion of the chromophoric DOM (CDOM) character can be described through an electronic interaction of charge transfer (CT) complexes. While much work has been done to understand the influence of CT on soil and aquatic reference standard DOM, little is known about the influence of CT in fresh terrestrially derived DOM. In this study, leaf litter leachates from three tree species were treated (reduced) with sodium borohydride to determine the contribution of CT on a source of fresh terrestrial DOM. Leaf litter was sampled four times through decomposition under natural (field) conditions to determine the influence of degradation on response to borohydride treatment. Leaf litter CDOM displayed a unique loss of UVB absorption following borohydride treatment, as well as a homogenizing effect on fluorescence emission character. Humification index (HIX) differentiated Elliot Soil Humic Acid and Suwannee River Fulvic Acid from leaf litter leachates. However, biological index (BIX), and spectral slope metrics were not able to differentiate leaf leachates from these reference standards. Apparent quantum yields were similar in magnitude between leaf leachates and reference standards, although leaf leachate spectra displayed features not evident in reference standards. These results help understand the origins of DOM optical properties and associated quantitative indices in freshly sourced terrestrial material. Overall, these results suggest that even at the initial stages of decomposition, terrestrial CDOM exhibits optical characteristics and responses to removal of electron accepting ketones and aldehydes, through borohydride treatment, similar to more processed CDOM.