Concentration–discharge (C‐Q) relationships reflect material sources, storage, reaction, proximity, and transport in catchments. Differences in hydrologic pathways and connectivity influence observed C‐Q patterns at the catchment outlet. We examined solute and sediment C‐Q relationships at event and interannual timescales in a small mid‐Atlantic (USA) catchment. We found systematic differences in the C‐Q behaviour of geogenic/exogenous solutes (e.g., calcium and nitrate), biologically associated solutes (e.g., dissolved organic carbon), and particulate materials (e.g., total suspended solids). Negative log(C)–log(Q) regression slopes, indicating dilution, were common for geogenic solutes whereas positive slopes, indicating concentration increase, were common for biologically associated solutes. Biologically associated solutes often exhibited counterclockwise hysteresis during events whereas geogenic solutes exhibited clockwise hysteresis. Across event and interannual timescales, solute C‐Q patterns are linked to the spatial distribution of hydrologic sources and the timing and sequence of hydro‐biogeochemical source contributions to the stream. Groundwater is the primary source of stormflow during the earliest and latest stages of events, whereas precipitation and soil water become increasingly connected to the stream near peakflow. This sequence and timing of flowpath connectivity results in dilution and clockwise hysteresis for geogenic/exogenous solutes and concentration increase and counterclockwise hysteresis for biologically associated solutes. Particulate materials demonstrated positive C‐Q slopes over the long‐term and clockwise hysteresis during individual events. Drivers of particulate and solute C‐Q relationships differ, based on longitudinal and lateral expansion of active channels and changing shear stresses with increasing flows. Although important distinctions exist between the drivers of solute and sediment C‐Q relationships, overall solute and sediment C‐Q patterns at event and interannual timescales reflect consistent catchment hydro‐biogeochemical processes.

Increased deposition of reactive atmospheric N has resulted in the nitrogen saturation of many forested catchments worldwide. Isotope-based studies from multiple forest sites report low proportions (mean 5 10%) of unprocessed atmospheric nitrate in streams during baseflow, regardless of N deposition or nitrate export rates. Given similar proportions of atmospheric nitrate in baseflow across a variety of sites and forest types, it is important to address the postdepositional drivers and processes that affect atmospheric nitrate transport and fate within catchments. In a meta-analysis of stable isotope-based studies, we examined the influence of methodological, biological, and hydrologic drivers on the export of atmospheric nitrate from forests. The d values tended to increase with increasing baseflow discharge at all sites examined. To explain these differences, we present a conceptual model of hydrologic flowpath characteristics (e.g., saturation overland flow versus subsurface stormflow) that considers the influence of topography on landscape-stream hydrologic connectivity and delivery of unprocessed atmospheric nitrate to streams. Methodological biases resulting from differences in sampling frequency and stable isotope analytical techniques may further influence the perceived degree of unprocessed atmospheric nitrate export. Synthesis of results from numerous isotope-based studies shows that small proportions of unprocessed atmospheric nitrate are common in baseflow. However, hydrologic, topographic, and methodological factors are important drivers of actual or perceived elevated contributions of unprocessed atmospheric nitrate to streams.

Nitrogen (N) deposition affects forest biogeochemical cycles worldwide, often contributing to N saturation. Using long-term (>30-year) records of stream nitrate (NO 3 -) concentrations at Fernow Experimental Forest (West Virginia, USA), we classified four watersheds into N saturation stages ranging from Stage 0 (N-limited) to Stage 3 (Nsaturated). We quantified NO 3 -contributions from atmospheric and microbial sources using d 15 N, d 18 O, and D 17 O of NO 3 -and characterized the concentrations and isotopes of NO 3 -in precipitation. Despite receiving identical atmospheric inputs, the proportions of atmospheric NO 3 -in streams averaged from 7 to 10% in the hardwood watersheds (stages 1, 2, and 3) and 54% in the conifer watershed (Stage 0). This suggests that the hardwood watersheds may be less responsive to future reductions in N deposition than the conifer watershed, at least in the short term. As shown in other studies, atmospheric NO 3 -proportions were higher during stormflow. Despite large proportions of atmospheric NO 3 -in the Stage 0 stream, total atmospheric NO 3 --N flux from this watershed (2.9 g ha -1 ) was lower than fluxes in the other watersheds (range = 117.8-338.5 g ha -1 ). Seasonal patterns of d 15 N-NO 3 -in the hardwood watersheds suggest enrichment of the soil NO 3 -pool during the growing season due to plant uptake. In all watersheds, d 18 O-based mixing models over-estimated atmospheric NO 3 -contributions to streams by up to 12% compared to D 17 O-based estimates. Our results highlight the importance of atmospheric deposition as a NO 3 -source in low-concentration streams and demonstrate the advantage of using D 17 O-NO 3 -over d 18 O-NO 3 -for NO 3 -source apportionment.

Little is known about the regional extent and variability of nitrate from atmospheric deposition that is transported to streams without biological processing in forests. We measured water chemistry and isotopic tracers (δ18O and δ15N) of nitrate sources across the Northern Forest Region of the U.S. and Canada and reanalyzed data from other studies to determine when, where, and how unprocessed atmospheric nitrate was transported in catchments. These inputs were more widespread and numerous than commonly recognized, but with high spatial and temporal variability. Only 6 of 32 streams had high fractions (>20%) of unprocessed atmospheric nitrate during baseflow. Seventeen had high fractions during stormflow or snowmelt, which corresponded to large fractions in near-surface soil waters or groundwaters, but not deep groundwater. The remaining 10 streams occasionally had some (<20%) unprocessed atmospheric nitrate during stormflow or baseflow. Large, sporadic events may continue to be cryptic due to atmospheric deposition variation among storms and a near complete lack of monitoring for these events. A general lack of observance may bias perceptions of occurrence; sustained monitoring of chronic nitrogen pollution effects on forests with nitrate source apportionments may offer insights needed to advance the science as well as assess regulatory and management schemes.

Sediment fingerprinting techniques are increasingly used to characterize the sources and transport processes of particulate materials in surface waters. However, consensus on the use of biologically labile compounds such as organic carbon and nitrogen for sediment fingerprinting remains elusive. We used multiple biogeochemical characteristics of suspended particulate material (SPM) to characterize the differences in formation and transport processes of these materials during storm events ranging in size from small seasonal rainfall events to hurricanes and tropical storms in a small mid‐Atlantic watershed. During storms, particle surface area, percent organic C, percent organic N, percent Fe, and percent Al of SPM decreased with increasing discharge; these contents were lowest during the extreme events Hurricane Sandy, Hurricane Irene, and Tropical Storm Lee. Conversely, SPM C:N values during these storms were among the highest of all samples, and C:N generally increased with discharge. End‐member mixing analysis indicated that organic matter and metal contents of SPM collected during high event flows were well described by materials collected from erosional source areas throughout the watershed, while SPM collected during low event flows fell outside of the end‐member mixing space. This suggests that physical transport processes govern SPM export primarily from surface and fluvial areas during high flows, while in‐stream biogeochemical processes become increasingly important contributors to SPM at lower flows.

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