Abstract. 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 (Rp; the sum of the local DOC production rates in individual grid cells) and export rate (Re; the product of the concentration and discharge at the stream outlet, or load). Results showed that daily Rp varied by less than an order of magnitude, primarily depending on seasonal temperature. In contrast, daily Re 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 Rp to its maximum but Re 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 Re peaked as the stream reconnected with uphill and Rp 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.

The shallow and deep hypothesis suggests that stream concentration‐discharge (CQ) relationships are shaped by distinct source waters from different depths. Under this hypothesis, baseflows are typically dominated by groundwater and mostly reflect groundwater chemistry, whereas high flows are typically dominated by shallow soil water and mostly reflect soil water chemistry. Aspects of this hypothesis draw on applications like end member mixing analyses and hydrograph separation, yet direct data support for the hypothesis remains scarce. This work tests the shallow and deep hypothesis using co‐located measurements of soil water, groundwater, and streamwater chemistry at two intensively monitored sites, the W‐9 catchment at Sleepers River (Vermont, United States) and the Hafren catchment at Plynlimon (Wales). At both sites, depth profiles of subsurface water chemistry and stream CQ relationships for the 10 solutes analyzed are broadly consistent with the hypothesis. Solutes that are more abundant at depth (e.g., calcium) exhibit dilution patterns (concentration decreases with increasing discharge). Conversely, solutes enriched in shallow soils (e.g., nitrate) generally exhibit flushing patterns (concentration increases with increasing discharge). The hypothesis may hold broadly true for catchments that share such biogeochemical stratifications in the subsurface. Soil water and groundwater chemistries were estimated from high‐ and low‐flow stream chemistries with average relative errors ranging from 24% to 82%. This indicates that streams mirror subsurface waters: stream chemistry can be used to infer scarcely measured subsurface water chemistry, especially where there are distinct shallow and deep end members.

Given the variable biogeochemical, physical, and hydrological processes driving fluvial sediment and nutrient export, the water science and management communities need data‐driven methods to identify regions prone to production and transport under variable hydrometeorological conditions. We use Bayesian analysis to segment concentration‐discharge linear regression models for total suspended solids (TSS) and particulate and dissolved phosphorus (PP, DP) using 22 years of monitoring data from 18 Lake Champlain watersheds. Bayesian inference was leveraged to estimate segmented regression model parameters and identify threshold position. The identified threshold positions demonstrated a considerable range below and above the median discharge—which has been used previously as the default breakpoint in segmented regression models to discern differences between pre and post‐threshold export regimes. We then applied a Self‐Organizing Map (SOM), which partitioned the watersheds into clusters of TSS, PP, and DP export regimes using watershed characteristics, as well as Bayesian regression intercepts and slopes. A SOM defined two clusters of high‐flux basins, one where PP flux was predominantly episodic and hydrologically driven; and another in which the sediment and nutrient sourcing and mobilization were more bimodal, resulting from both hydrologic processes at post‐threshold discharges and reactive processes (e.g., nutrient cycling or lateral/vertical exchanges of fine sediment) at prethreshold discharges. A separate DP SOM defined two high‐flux clusters exhibiting a bimodal concentration‐discharge response, but driven by differing land use. Our novel framework shows promise as a tool with broad management application that provides insights into landscape drivers of riverine solute and sediment export.

The East Antarctic Ice Sheet (EAIS) is the largest potential contributor to sea-level rise. However, efforts to predict the future evolution of the EAIS are hindered by uncertainty in how it responded to past warm periods, for example, during the Pliocene epoch (5.3 to 2.6 million years ago), when atmospheric carbon dioxide concentrations were last higher than 400 parts per million. Geological evidence indicates that some marine-based portions of the EAIS and the West Antarctic Ice Sheet retreated during parts of the Pliocene, but it remains unclear whether ice grounded above sea level also experienced retreat. This uncertainty persists because global sea-level estimates for the Pliocene have large uncertainties and cannot be used to rule out substantial terrestrial ice loss , and also because direct geological evidence bearing on past ice retreat on land is lacking. Here we show that land-based sectors of the EAIS that drain into the Ross Sea have been stable throughout the past eight million years. We base this conclusion on the extremely low concentrations of cosmogenicBe and Al isotopes found in quartz sand extracted from a land-proximal marine sediment core. This sediment had been eroded from the continent, and its low levels of cosmogenic nuclides indicate that it experienced only minimal exposure to cosmic radiation, suggesting that the sediment source regions were covered in ice. These findings indicate that atmospheric warming during the past eight million years was insufficient to cause widespread or long-lasting meltback of the EAIS margin onto land. We suggest that variations in Antarctic ice volume in response to the range of global temperatures experienced over this period-up to 2-3 degrees Celsius above preindustrial temperatures , corresponding to future scenarios involving carbon dioxide concentrations of between 400 and 500 parts per million-were instead driven mostly by the retreat of marine ice margins, in agreement with the latest models.

Roads in rural, upland landscapes are important sources of runoff and sediment to waterways. The downstream effects of these sources should be related to the connectivity of roads to receiving waters. Recent studies have explored this idea, but only simple metrics have been used to characterize connectivity and few studies have quantified the downstream effects of road–stream connectivity on sediment or solute budgets and channel morphology. In this study, we evaluated traditional and newly developed connectivity metrics that utilized features of landscape position and delivery pathway to characterize road–stream connectivity in upland settings. Using data on stream geomorphic conditions developed by the Vermont Agency of Natural Resources (Montpelier, VT), we related road connectivity metrics to channel condition on a set of 101 forested, upland streams with minimal development other than predominantly gravel road networks. Logistic regression indicated that measures of road density, proximity and orientation successfully distinguished among categories of stream geomorphic condition at multiple geographic scales. Discriminant function analysis using a set of inherent channel characteristics combined with road connectivity metrics derived at the reach corridor scale successfully distinguished channel condition for over 70% of the channels evaluated. This research contributes to efforts to evaluate the cumulative downstream effects of roads on stream channels and aquatic resources and provides a new means of watershed assessment to derive metrics that can be used to predict channel condition. Copyright © 2014 John Wiley & Sons, Ltd.

Stream water pH and composition are widely used to monitor ongoing recovery from the deposition of strong anthropogenic acids in many forested headwater catchments in the northeastern United States. However, stream water composition is a function of highly complex and coupled processes, flowpaths, and variations in soil and bedrock composition. Spatial heterogeneity is especially pronounced in headwater catchments with steep topography, potentially limiting stream water composition as an indicator of changes in critical zone (CZ) dynamics during system recovery. To investigate the link between catchment characteristics, landscape position, and stream water composition we used long-term data from the Sleepers River Research Watershed (SRRW) in northeastern Vermont. We investigated trends with time in stream water and trends with time, depth, and landscape position (upslope, midslope, and riparian zone) in groundwater (GW) and soil solution. We further determined soil elemental composition and mineralogy on archived (1996) and modern (2017) soil samples to assess changes in composition with time. SRRW is inherently well-buffered by calcite in bedrock and till, but soils had become acidified and are now recovering from acidification. Although base cations, especially Ca, decrease progressively with time in GW, riparian soils have become more enriched in Ca, due to a mixture of lateral and vertical transfers. At the same time stream water Ca fluxes increased over the past two decades, likely due to the leaching of (transient) legacy Ca from riparian zones and increased water fluxes. The stream water response therefore reflects the dynamic changes in soil chemistry, flow routing and water inputs.

Abstract. 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. We applied the catchment-scale hydro-biogeochemical reactive transport model BioRT-Flux-PIHM to simulate the DOC dynamics. We estimated the daily DOC production rate (Rp; the sum of local DOC production rates in individual modeling grid cell) and the daily DOC export rate (Re; the product of concentration and discharge at the stream outlet) to downstream ecosystems. Simulations showed that Rp varied by less than an order of magnitude and primarily hinged on seasonal temperature change. In contrast, Re varied by more than three orders of magnitude with a strong dependence on discharge and hydrological connectivity. During summer, high temperatures led to high atmospheric water demand (and evapotranspiration) that dried and disconnected hillslope to stream. Rp reached its maximum but Re was at its minimum. The stream only exported DOC from the organic-poor groundwater and from soil water in the narrow organic-rich swales with enriched DOC such that DOC accumulated in the catchment. During the wet period (winter and spring), Rp reached its minimum but Re peaked because the stream was re-connected to a greater uphill area, flushing out the stored DOC. The model reproduced the observed concentration discharge (C–Q) relationship characterized by a flushing-dilution pattern with a rise in concentrations to a maximum (flushing) at a threshold discharge and then followed a general dilution with concentrations decreasing with discharge. This pattern was explained by the comparable contribution of organic-poor deeper groundwater and soil water from organic-rich swales at the minimum flow, maximized percentage contribution of soil water from organic-rich swales at the low flow regime, and increased contribution of uphill soil water interflow from uphill with less DOC at the high flow regime. This pattern persisted regardless of DOC production rate as long as the contribution of deeper groundwater flow remained low ( 18 %, the flushing-dilution C–Q pattern shifted towards a flushing-only pattern with DOC concentrations increasing with discharge. This study illustrates the temporal asynchrony of DOC production, mostly controlled by temperature, and DOC export, primarily governed by hydrological flow paths at the catchment scale. The occurrence of warmer and more extreme hydrological events in the future could accentuate this asynchrony, with major lateral export of DOC dominated by a few major storm events whereas DOC is produced and stored in the catchment in the prolonged drought periods.

Abstract. Large sample datasets are transforming hypothesis testing and model fidelity in the catchment sciences, but few large stream water chemistry datasets exist with complementary streamflow, meteorology, and catchment physiographic attributes. Here, we pair atmospheric deposition and water chemistry related information with the existing CAMELS (Catchment Attributes and Meteorology for Large-sample Studies) dataset. The newly developed dataset, CAMELS-Chem, comprises U.S. Geological Survey water chemistry data and instantaneous discharge over the period from 1980 through 2014 in 506 minimally impacted headwater catchments. The CAMELS-Chem dataset includes 18 common stream water chemistry constituents: Al, Ca, Cl, Dissolved Organic Carbon, Total Organic Carbon, HCO3, K, Mg, Na, Total Dissolved Nitrogen [nitrate + nitrite + ammonia + organic-N], Total Organic Nitrogen, NO3, Dissolved Oxygen, pH (field and lab), Si, SO4, and water temperature. We also provide an annual wet deposition loads from the National Atmospheric Deposition Program over the same catchments that includes: Ca, Cl, H, K, Mg, and Total Nitrogen from deposition [precipitation NO3 + NH4, dry deposition of particulate NH4, + NO3, and gaseous NH3], Na, NH4, NO3, SO₄. We release a paired instantaneous discharge (and mean daily discharge) measurement for all chemistry samples. To motivate wider use by the larger scientific community, we develop three example analyses: 1. Atmospheric-aquatic linkages using atmospheric and stream SO4 trends, 2. Hydrologic-biogeochemical linkages using concentration-discharge relations, and 3. Geological-biogeochemical linkages using weathering relations. The retrieval scripts and final dataset of > 412,801 individual stream water chemistry measurements are available to the wider scientific community for continued investigation.