Climate exerts a powerful influence on biological processes, but the effects of climate change on ecosystem nutrient flux and cycling are poorly resolved. Although rare, long-term records offer a unique opportunity to disentangle effects of climate from other anthropogenic influences. Here, we examine the longest and most complete record of watershed nutrient and climate dynamics available worldwide, which was collected at the Hubbard Brook Experimental Forest in the northeastern United States. We used empirical analyses and model calculations to distinguish between effects of climate change and past perturbations on the forest nitrogen (N) cycle. We find that climate alone cannot explain the occurrence of a dramatic >90% drop in watershed nitrate export over the past 46 y, despite longer growing seasons and higher soil temperatures. The strongest climate influence was an increase in soil temperature accompanied by a shift in paths of soil water flow within the watershed, but this effect explained, at best, only ∼40% of the nitrate decline. In contrast, at least 50–60% of the observed change in the N export could be explained by the long-lasting effect of forest cutting in the early 1900s on the N cycle of the soil and vegetation pools. Our analysis shows that historic events can obscure the influence of modern day stresses on the N cycle, even when analyses have the advantage of being informed by 0.5-century-long datasets. These findings raise fundamental questions about interpretations of long-term trends as a baseline for understanding how climate change influences complex ecosystems.

Lateral carbon flux through river networks is an important and poorly understood component of the global carbon budget. This work investigates how temperature and hydrology control the production and export of dissolved organic carbon (DOC) in the Susquehanna Shale Hills Critical Zone Observatory in Pennsylvania, USA. Using field measurements of daily stream discharge, evapotranspiration, and stream DOC concentration, we calibrated the catchment-scale biogeochemical reactive transport model BioRT-Flux-PIHM (Biogeochemical Reactive Transport–Flux–Penn State Integrated Hydrologic Model, BFP), which met the satisfactory standard of a Nash–Sutcliffe efficiency (NSE) value greater than 0.5. We used the calibrated model to estimate and compare the daily DOC production rates (R_p; the sum of the local DOC production rates in individual grid cells) and export rate (R_e; the product of the concentration and discharge at the stream outlet, or load). Results showed that daily R_p varied by less than an order of magnitude, primarily depending on seasonal temperature. In contrast, daily R_e varied by more than 3 orders of magnitude and was strongly associated with variation in discharge and hydrological connectivity. In summer, high temperature and evapotranspiration dried and disconnected hillslopes from the stream, driving R_p to its maximum but R_e to its minimum. During this period, the stream only exported DOC from the organic-poor groundwater and from organic-rich soil water in the swales bordering the stream. The DOC produced accumulated in hillslopes and was later flushed out during the wet and cold period (winter and spring) when R_e peaked as the stream reconnected with uphill and R_p reached its minimum. The model reproduced the observed concentration–discharge (C–Q) relationship characterized by an unusual flushing–dilution pattern with maximum concentrations at intermediate discharge, indicating three end-members of source waters. A sensitivity analysis indicated that this nonlinearity was caused by shifts in the relative contribution of different source waters to the stream under different flow conditions. At low discharge, stream water reflected the chemistry of organic-poor groundwater; at intermediate discharge, stream water was dominated by the organic-rich soil water from swales; at high discharge, the stream reflected uphill soil water with an intermediate DOC concentration. This pattern persisted regardless of the DOC production rate as long as the contribution of deeper groundwater flow remained low (<18 % of the streamflow). When groundwater flow increased above 18 %, comparable amounts of groundwater and swale soil water mixed in the stream and masked the high DOC concentration from swales. In that case, the C–Q patterns switched to a flushing-only pattern with increasing DOC concentration at high discharge. These results depict a conceptual model that the catchment serves as a producer and storage reservoir for DOC under hot and dry conditions and transitions into a DOC exporter under wet and cold conditions. This study also illustrates how different controls on DOC production and export – temperature and hydrological flow paths, respectively – can create temporal asynchrony at the catchment scale. Future warming and increasing hydrological extremes could accentuate this asynchrony, with DOC production occurring primarily during dry periods and lateral export of DOC dominating in major storm events.