Deconstructing the Effects of Flow on DOC, Nitrate, and Major Ion Interactions Using a High‐Frequency Aquatic Sensor Network

Streams provide a physical linkage between land and downstream river networks, delivering solutes derived from multiple catchment sources. We analyzed high-frequency time series of stream solutes to characterize the timing and magnitude of major ion, nutrient, and organic matter transport over event, seasonal, and annual timescales as well as to assess whether nitrate (NO2-) and dissolved organic carbon (DOC) transport are coupled in catchments, which would be expected if they are subject to similar biogeochemical controls throughout the watershed. Our data set includes in situ observations of NO2-, fluorescent dissolved organic matter (DOC proxy), and specific conductance spanning 2-4 years in 10 streams and rivers across New Hampshire, including observations of nearly 700 individual hydrologic events. We found a positive response of NO2- and DOC to flow in forested streams, but watershed development led to a negative relationship between NO2- and discharge, and thus a decoupling of the overall NO2- and DOC responses to flow. On event and seasonal timescales, NO2- and DOC consistently displayed different behaviors. For example, in several streams, FDOM yield was greatest during summer storms while NO2- yield was greatest during winter storms. Most streams had generalizable storm NO2- and DOC responses, but differences in the timing of NO2- and DOC transport suggest different catchment sources. Further, certain events, including rain-on-snow and summer storms following dry antecedent conditions, yielded disproportionate NO2- responses. High-frequency data allow for increased understanding of the processes controlling solute variability and will help reveal their responses to changing climatic regimes.