Ongoing increases in dissolved organic carbon are sustained by decreases in ionic strength rather than decreased acidity in waters recovering from acidic deposition.

Dissolved organic carbon (DOC) has received considerable attention in freshwater research, particularly since the early 2000s when increasing trends became apparent. However, remaining questions need to be resolved to address future effects of DOC on surface waters. This study was undertaken to determine (1) the relative importance of acidity and ionic strength in driving DOC increases in waters recovering from acidification and (2) the role played by long-term acid rain effects on soil. Data obtained from temporal and spatial monitoring of 142 headwater streams throughout the Adirondack region of New York (USA) were used to evaluate chemical relationships involving DOC. Year-round monitoring of three streams of differing acidification status were combined with intermittent stream surveys during spring snowmelt throughout this 24,243 km2 region that is recovering from acidification of soils and surface waters. Despite acidic deposition decreases reaching levels estimated for the early 1900s, DOC concentrations exhibited linear increases from the early 2000s through 2019. Ionic strength or conductivity showed consistent inverse relationships with DOC in all data comparisons from 2004‐05 to 2018‐19. In contrast, relationships between pH and DOC did not support increasing pH as an important factor in DOC increases. Inconsistent relationships between pH and DOC were due to strongly acidic organic acids that remain unprotonated throughout the pH range of these waters and limited weak-acid deprotonation below pH 6.2. Decreasing ionic strength increases DOC solubility by expanding the diffuse double layer, which fosters disaggregation of organic matter and dispersion of colloids. This affect controlled DOC solubilization below a pH of approximately 6.2. Distinguishing between ionic strength and pH effects is important because further large reductions in acidic deposition are not expected but continued soil-water dilution is likely from soil-Ca2+ depletion and the decreasing rate of Ca2+ leaching by SO 4 2− and NO 3 −, which are still being released from soil organic matter. Unlabelled Image • DOC in surface waters continues to increase despite low acid rain levels. • Decreases in ionic strength, not acidity are increasing soil carbon solubility. • Soil‑calcium depletion is a key factor in ongoing decreases in ionic strength. • Ionic strength decreases will continue driving further increases in DOC. • pH is not controlling DOC in drainage waters, DOC is instead controlling pH. [ABSTRACT FROM AUTHOR]