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Abstract 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 Machine‐learning models have been surprisingly successful at predicting stream solute concentrations, even for solutes without dedicated sensors. It would be extremely valuable if these models could predict solute concentrations in streams beyond the one in which they were trained. We assessed the generalisability of random forest models by training them in one or more streams and testing them in another. Models were made using grab sample and sensor data from 10 New Hampshire streams and rivers. As observed in previous studies, models trained in one stream were capable of accurately predicting solute concentrations in that stream. However, models trained on one stream produced inaccurate predictions of solute concentrations in other streams, with the exception of solutes measured by dedicated sensors (i.e., nitrate and dissolved organic carbon). Using data from multiple watersheds improved model results, but model performance was still worse than using the mean of the training dataset (Nash–Sutcliffe Efficiency < 0). Our results demonstrate that machine‐learning models thus far reliably predict solute concentrations only where trained, as differences in solute concentration patterns and sensor‐solute relationships limit their broader applicability. 

Abstract Stream fluxes are commonly reported without a complete accounting for uncertainty in the estimates, which makes it difficult to evaluate the significance of findings or to identify where to direct efforts to improve monitoring programs. At the Hubbard Brook Experimental Forest in the White Mountains of New Hampshire, USA, stream flow has been monitored continuously and solute concentrations have been sampled approximately weekly in small, gaged headwater streams since 1963, yet comprehensive uncertainty analyses have not been reported. We propagated uncertainty in the stage height–discharge relationship, watershed area, analytical chemistry, the concentration–discharge relationship used to interpolate solute concentrations, and the streamflow gap‐filling procedure to estimate uncertainty for both streamflow and solute fluxes for a recent 6‐year period (2013–2018) using a Monte Carlo approach. As a percentage of solute fluxes, uncertainty was highest for NH₄⁺(34%), total dissolved nitrogen (8.8%), NO₃⁻(8.1%), and K⁺(7.4%), and lowest for dissolved organic carbon (3.7%), SO₄²⁻(4.0%), and Mg²⁺(4.4%). In units of flux, uncertainties were highest for solutes in highest concentration (Si, DOC, SO₄²⁻, and Na⁺) and lowest for those lowest in concentration (H⁺and NH₄⁺). Laboratory analysis of solute concentration was a greater source of uncertainty than streamflow for solute flux, with the exception of DOC. Our results suggest that uncertainty in solute fluxes could be reduced with more precise measurements of solute concentrations. Additionally, more discharge measurements during high flows are needed to better characterize the stage‐discharge relationship. Quantifying uncertainty in streamflow and element export is important because it allows for determination of significance of differences in fluxes, which can be used to assess watershed response to disturbance and environmental change.