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.
This content will become publicly available on June 1, 2025
Understanding controls on solute export to streams is challenging because heterogeneous catchments can respond uniquely to drivers of environmental change. To understand general solute export patterns, we used a large‐scale inductive approach to evaluate concentration–discharge (C–Q) metrics across catchments spanning a broad range of catchment attributes and hydroclimatic drivers. We leveraged paired C–Q data for 11 solutes from CAMELS‐Chem, a database built upon an existing dataset of catchment and hydroclimatic attributes from relatively undisturbed catchments across the contiguous USA. Because C–Q relationships with Q thresholds reflect a shift in solute export dynamics and are poorly characterized across solutes and diverse catchments, we analysed C–Q relationships using Bayesian segmented regression to quantify Q thresholds in the C–Q relationship. Threshold responses were rare, representing only 12% of C–Q relationships, 56% of which occurred for solutes predominantly sourced from bedrock. Further, solutes were dominated by one or two C–Q patterns that reflected vertical solute–source distributions. Specifically, solutes predominantly sourced from bedrock had diluting C–Q responses in 43%–70% of catchments, and solutes predominantly sourced from soils had more enrichment responses in 35%–51% of catchments. We also linked C–Q relationships to catchment and hydroclimatic attributes to understand controls on export patterns. The relationships were generally weak despite the diversity of solutes and attribute types considered. However, catchment and hydroclimatic attributes in the central USA typically drove the most divergent export behaviour for solutes. Further, we illustrate how our inductive approach generated new hypotheses that can be tested at discrete, representative catchments using deductive approaches to better understand the processes underlying solute export patterns. Finally, given these long‐term C–Q relationships are from minimally disturbed catchments, our findings can be used as benchmarks for change in more disturbed catchments.
more » « less- Award ID(s):
- 2033995
- PAR ID:
- 10562727
- Publisher / Repository:
- Wiley
- Date Published:
- Journal Name:
- Hydrological Processes
- Volume:
- 38
- Issue:
- 6
- ISSN:
- 0885-6087
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Abstract -
Abstract Floods are dominant controls on export of solutes from catchments. In contrast, low‐flow periods such as droughts are potentially dominant control points for biogeochemical processing, enhancing spatiotemporal variation in solute concentrations, stream metabolism, and nutrient uptake. Using complementary time series (i.e., an Eulerian reference frame) and longitudinal profiling (i.e., a Lagrangian reference frame), we investigated hydrologic controls on temporal and spatial variation in solute flux and metabolism in the Lower Santa Fe River (FL, USA), where highly colored surface water mixes with exceptionally clear groundwater from springs. Gage measurements suggest groundwater inputs ranged from <1% (during extreme floods) to 86% (during extreme drought) of total discharge (
Q ). Mass transport of most solutes was dominated by high‐Q periods. Most soluteC ‐Q relationships exhibited statistically significant slope breakpoints near the transition between surface and groundwater dominance. In particular, parameters controlling water column light attenuation were chemostatic above medianQ but markedly reduced at lowQ . As a result, river metabolism and assimilatory nitrate (NO3−) uptake were consistently suppressed at highQ and enhanced at lowQ , with greater variability in response to drivers other than water column light transmittance. Spatial variation in solute concentrations was also enhanced at lowQ , induced by discrete groundwater inflow and biogeochemical processing along the reach. Contrasting reference frames yielded corroborative evidence for transport dominance at highQ , which damps spatiotemporal heterogeneity. In contrast, low‐Q periods enable localized mixing controls on solute concentrations and high rates of metabolism and nutrient processing that increase spatiotemporal variability. -
Abstract Processes that drive variability in catchment solute sourcing, transformation, and transport can be investigated using concentration–discharge (C–Q) relationships. These relationships reflect catchment and in‐stream processes operating across nested temporal scales, incorporating both short and long‐term patterns. Scientists can therefore leverage catchment‐scale C–Q datasets to identify and distinguish among the underlying meteorological, biological, and geological processes that drive solute export patterns from catchments and influence the shape of their respective C–Q relationships. We have synthesized current knowledge regarding the influence of biological, geological, and meteorological processes on C–Q patterns for various solute types across diel to decadal time scales. We identify cross‐scale linkages and tools researchers can use to explore these interactions across time scales. Finally, we identify knowledge gaps in our understanding of C–Q temporal dynamics as reflections of catchment and in‐stream processes. We also lay the foundation for developing an integrated approach to investigate cross‐scale linkages in the temporal dynamics of C–Q relationships, reflecting catchment biogeochemical processes and the effects of environmental change on water quality.
This article is categorized under:
Science of Water > Hydrological Processes
Science of Water > Water Quality
Science of Water > Water and Environmental Change
-
Abstract. Solute concentrations in stream water vary with discharge in patterns that record complex feedbacks between hydrologic and biogeochemical processes. In a comparison of three shale-underlain headwater catchments located in Pennsylvania, USA (the forested Shale Hills Critical Zone Observatory), and Wales, UK (the peatland-dominated Upper Hafren and forest-dominated Upper Hore catchments in the Plynlimon forest), dissimilar concentration–discharge (C–Q) behaviors are best explained by contrasting landscape distributions of soil solution chemistry – especially dissolved organic carbon (DOC) – that have been established by patterns of vegetation and soil organic matter (SOM). Specifically, elements that are concentrated in organic-rich soils due to biotic cycling (Mn, Ca, K) or that form strong complexes with DOC (Fe, Al) are spatially heterogeneous in pore waters because organic matter is heterogeneously distributed across the catchments. These solutes exhibit non-chemostatic behavior in the streams, and solute concentrations either decrease (Shale Hills) or increase (Plynlimon) with increasing discharge. In contrast, solutes that are concentrated in soil minerals and form only weak complexes with DOC (Na, Mg, Si) are spatially homogeneous in pore waters across each catchment. These solutes are chemostatic in that their stream concentrations vary little with stream discharge, likely because these solutes are released quickly from exchange sites in the soils during rainfall events. Furthermore, concentration–discharge relationships of non-chemostatic solutes changed following tree harvest in the Upper Hore catchment in Plynlimon, while no changes were observed for chemostatic solutes, underscoring the role of vegetation in regulating the concentrations of certain elements in the stream. These results indicate that differences in the hydrologic connectivity of organic-rich soils to the stream drive differences in concentration behavior between catchments. As such, in catchments where SOM is dominantly in lowlands (e.g., Shale Hills), we infer that non-chemostatic elements associated with organic matter are released to the stream early during rainfall events, whereas in catchments where SOM is dominantly in uplands (e.g., Plynlimon), these non-chemostatic elements are released later during rainfall events. The distribution of SOM across the landscape is thus a key component for predictive models of solute transport in headwater catchments.
-
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.more » « less