Long-Term Experimental Acidification Drives Watershed Scale Shift in Dissolved Organic Matter Composition and Flux

Over the last several decades dissolved organic carbon concentrations (DOC) in surface waters have increased throughout much of the northern hemisphere. Several hypotheses have been proposed regarding the drivers of this phenomenon including decreased sulfur (S) deposition working via an acidity- change mechanism. Using fluorescence spectroscopy and data from two long-term (24+ years at completion of this study) whole watershed acidification experiments, that is, the Bear Brook Watershed in Maine (BBWM) and Fernow Experimental Forest in West Virginia (FEF) allowed us to control for factors other than the acidity-change mechanism (e.g., differing vegetation, shifting climate), resulting in the first study we are aware of where the acidity change mechanism could be experimentally isolated at the whole ecosystem and decadal scales as the driver of shifts in DOM dynamics. The multidecadal record of stream chemistry at BBWM demonstrates a significantly lower DOC concentration in the treated compared to the reference watershed. Additionally, at both BBWM and FEF we found significant and sustained differences in stream fluorescence index (FI) between the treated and reference watersheds, with the reference watersheds demonstrating a stronger terrestrial DOM signature. These data, coupled with evidence of pH shifts in upper soil horizons support the hypotheses that declines in S deposition are driving changes in the solubility of soil organic matter and increased flux of terrestrial DOC to water bodies.