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Temporal patterns in chemistry of headwater streams reflect responses of water and elemental cycles to perturbations occurring at local to global scales. We evaluated multi-scale temporal patterns in up to 32 y of monthly observations of stream chemistry (ammonium, calcium, dissolved organic carbon, nitrate, total dissolved phosphorus, and sulfate) in 22 reference catchments within the northern temperate zone of North America. Multivariate autoregressive state-space (MARSS) models were applied to quantify patterns at multi-decadal, seasonal, and shorter intervals during a period that encompassed warming climate, seasonal changes in precipitation, and regional declines in atmospheric deposition. Significant long-term trends in solute concentrations within a subset of the catchments were consistent with recovery from atmospheric deposition (e.g., calcium, nitrate, sulfate) and increased precipitation (e.g., dissolved organic carbon). Lack of evidence for multi-decadal trends in most catchments suggests resilience of northern temperate ecosystems or that subtle net effects of simultaneous changes in climate and disturbance regimes do not result in directional trends. Synchronous seasonal oscillations of solute concentrations occurred across many catchments, reflecting shared climate and biotic drivers of seasonality within the northern temperate zone. Despite shared patterns among catchments at a seasonal scale, multi-scale temporal patterns were statistically distinct among even adjacent headwater catchments, implying that local attributes of headwater catchments modify the signals imparted by atmospheric phenomena and regional disturbances. To effectively characterize hydrologic and biogeochemical responses to changing climate and disturbance regimes, catchment monitoring programs could include multiple streams with contributing areas that encompass regional heterogeneity in vegetation, topography, and elevation. Overall, detection of long-term patterns and trends requires monitoring multiple catchments at a frequency that captures periodic variation (e.g., seasonality) and a duration encompassing the perturbations of interest. 

Abstract The hydrological effects of climate change are documented in many regions; however, climate-driven impacts to the source and transport of river nutrients remain poorly understood. Understanding the factors controlling nutrient dynamics across river systems is critical to preserve ecosystem function yet challenging given the complexity of landscape and climate interactions. Here, we harness a large regional dataset of nitrate (NO₃^–) yield, concentration, and isotopic composition (δ¹⁵N and δ¹⁸O) to evaluate the strength of hydroclimate and landscape variables in controlling the seasonal source and transport of NO₃^–. We show that hydroclimate strongly influenced the seasonality of river NO₃^–, producing distinct, source-dependent NO₃^–regimes across rivers from two mountain ranges. Riverine responses to hydroclimate were also constrained by watershed-scale topographic features, demonstrating that while regional climate strongly influences the timing of river NO₃^–transport, watershed topography plays a distinct role in mediating the sensitivity of river NO₃^–dynamics to future change. 

Temporal patterns in stream chemistry provide integrated signals describing the hydrological and ecological state of whole catchments. However, stream chemistry integrates multi-scale signals of processes occurring in both the catchment and stream. Deconvoluting these signals could identify mechanisms of solute transport and transformation and provide a basis for monitoring ecosystem change. We applied trend analysis, wavelet decomposition, multivariate autoregressive state-space modeling, and analysis of concentration–discharge relationships to assess temporal patterns in high-frequency (15 min) stream chemistry from permafrost-influenced boreal catchments in Interior Alaska at diel, storm, and seasonal time scales. We compared catchments that varied in spatial extent of permafrost to identify characteristic biogeochemical signals. Catchments with higher spatial extents of permafrost were characterized by increasing nitrate concentration through the thaw season, an abrupt increase in nitrate and fluorescent dissolved organic matter (fDOM) and declining conductivity in late summer, and flushing of nitrate and fDOM during summer rainstorms. In contrast, these patterns were absent, of lower magnitude, or reversed in catchments with lower permafrost extent. Solute dynamics revealed a positive influence of permafrost on fDOM export and the role of shallow, seasonally dynamic flowpaths in delivering solutes from high-permafrost catchments to streams. Lower spatial extent of permafrost resulted in static delivery of nitrate and limited transport of fDOM to streams. Shifts in concentration–discharge relationships and seasonal trends in stream chemistry toward less temporally dynamic patterns might therefore indicate reorganized catchment hydrology and biogeochemistry due to permafrost thaw.