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Abstract River networks play a crucial role in the global carbon cycle, as relevant sources of carbon dioxide (CO₂) to the atmosphere. Advancements in high‐frequency monitoring in aquatic environments have enabled measurement of dissolved CO₂concentration at temporal resolutions essential for studying carbon variability and evasion from these dynamic ecosystems. Here, we describe the adaptation, deployment, and validation of an open‐source and relatively low‐cost in situpCO₂sensor system for lotic ecosystems, the lotic‐SIPCO2. We tested the lotic‐SIPCO2 in 10 streams that spanned a range of land cover and basin size. Key system adaptations for lotic environments included prevention of biofouling, configuration for variable stage height, and reduction of headspace equilibration time. We then examined which input parameters contribute the most to uncertainty in estimating CO₂emission rates and found scaling factors related to the gas exchange velocity were the most influential when CO₂concentration was significantly above saturation. Near saturation, sensor measurement ofpCO₂contributed most to uncertainty in estimating CO₂emissions. We also found high‐frequency measurements ofpCO₂were not necessary to accurately estimate median emission rates given the CO₂regimes of our streams, but daily to weekly sampling was sufficient. High‐frequency measurements ofpCO₂remain valuable for exploring in‐stream metabolic variability, source partitioning, and storm event dynamics. Our adaptations to the SIPCO2 offer a relatively affordable and robust means of monitoring dissolved CO₂in lotic ecosystems. Our findings demonstrate priorities and related considerations in the design of monitoring projects of dissolved CO₂and CO₂evasion dynamics more broadly. 

Abstract Fluvial silicon (Si) plays a critical role in controlling primary production, water quality, and carbon sequestration through supporting freshwater and marine diatom communities. Geological, biogeochemical, and hydrological processes, as well as climate and land use, dictate the amount of Si exported by streams. Understanding Si regimes—the seasonal patterns of Si concentrations—can help identify processes driving Si export. We analyzed Si concentrations from over 200 stream sites across the Northern Hemisphere to establish distinct Si regimes and evaluated how often sites moved among regimes over their period of record. We observed five distinct regimes across diverse stream sites, with nearly 60% of sites exhibiting multiple regime types over time. Our results indicate greater spatial and interannual variability in Si seasonality than previously recognized and highlight the need to characterize the watershed and climate variables that affect Si cycling across diverse ecosystems. 

Abstract Riverine exports of silicon (Si) influence global carbon cycling through the growth of marine diatoms, which account for ∼25% of global primary production. Climate change will likely alter river Si exports in biome‐specific ways due to interacting shifts in chemical weathering rates, hydrologic connectivity, and metabolic processes in aquatic and terrestrial systems. Nonetheless, factors driving long‐term changes in Si exports remain unexplored at local, regional, and global scales. We evaluated how concentrations and yields of dissolved Si (DSi) changed over the last several decades of rapid climate warming using long‐term data sets from 60 rivers and streams spanning the globe (e.g., Antarctic, tropical, temperate, boreal, alpine, Arctic systems). We show that widespread changes in river DSi concentration and yield have occurred, with the most substantial shifts occurring in alpine and polar regions. The magnitude and direction of trends varied within and among biomes, were most strongly associated with differences in land cover, and were often independent of changes in river discharge. These findings indicate that there are likely diverse mechanisms driving change in river Si biogeochemistry that span the land‐water interface, which may include glacial melt, changes in terrestrial vegetation, and river productivity. Finally, trends were often stronger in months outside of the growing season, particularly in temperate and boreal systems, demonstrating a potentially important role of shifting seasonality for the flux of Si from rivers. Our results have implications for the timing and magnitude of silica processing in rivers and its delivery to global oceans. 

Abstract River networks regulate carbon and nutrient exchange between continents, atmosphere, and oceans. However, contributions of riverine processing are poorly constrained at continental scales. Scaling relationships of cumulative biogeochemical function with watershed size (allometric scaling) provide an approach for quantifying the contributions of fluvial networks in the Earth system. Here we show that allometric scaling of cumulative riverine function with watershed area ranges from linear to superlinear, with scaling exponents constrained by network shape, hydrological conditions, and biogeochemical process rates. Allometric scaling is superlinear for processes that are largely independent of substrate concentration (e.g., gross primary production) due to superlinear scaling of river network surface area with watershed area. Allometric scaling for typically substrate-limited processes (e.g., denitrification) is linear in river networks with high biogeochemical activity or low river discharge but becomes increasingly superlinear under lower biogeochemical activity or high discharge, conditions that are widely prevalent in river networks. The frequent occurrence of superlinear scaling indicates that biogeochemical activity in large rivers contributes disproportionately to the function of river networks in the Earth system. 

Nitrogen (N) is a critical element in many ecological and biogeochemical processes in forest ecosystems. Cycling of N is sensitive to changes in climate, atmospheric carbon dioxide (CO2) concentrations, and air pollution. Streamwater nitrate draining a forested ecosystem can indicate how an ecosystem is responding to these changes. We observed a pulse in streamwater nitrate concentration and export at a long-term forest research site in eastern North America that resulted in a 10-fold increase in nitrate export compared to observations over the prior decade. The pulse in streamwater nitrate occurred in a reference catchment in the 2013 water year, but was not associated with a distinct disturbance event. We analyzed a suite of environmental variables to explore possible causes. The correlation between each environmental variable and streamwater nitrate concentration was consistently higher when we accounted for the antecedent conditions of the variable prior to a given streamwater observation. In most cases, the optimal antecedent period exceeded two years. We assessed the most important variables for predicting streamwater nitrate concentration by training a machine learning model to predict streamwater nitrate concentration in the years preceding and during the streamwater nitrate pulse. The results of the correlation and machine learning analyses suggest that the pulsed increase in streamwater nitrate resulted from both (1) decreased plant uptake due to lower terrestrial gross primary production, possibly due to increased soil frost or reduced solar radiation or both; and (2) increased net N mineralization and nitrification due to warm temperatures from 2010 to 2013. Additionally, variables associated with hydrological transport of nitrate, such as maximum stream discharge, emerged as important, suggesting that hydrology played a role in the pulse. Overall, our analyses indicate that the streamwater nitrate pulse was caused by a combination of factors that occurred in the years prior to the pulse, not a single disturbance event. 

We utilize a coupled economy–agroecology–hydrology modeling framework to capture the cascading impacts of climate change mitigation policy on agriculture and the resulting water quality cobenefits. We analyze a policy that assigns a range of United States government’s social cost of carbon estimates ($51, $76, and $152/ton of CO₂-equivalents) to fossil fuel–based CO₂emissions. This policy raises energy costs and, importantly for agriculture, boosts the price of nitrogen fertilizer production. At the highest carbon price, US carbon emissions are reduced by about 50%, and nitrogen fertilizer prices rise by about 90%, leading to an approximate 15% reduction in fertilizer applications for corn production across the Mississippi River Basin. Corn and soybean production declines by about 7%, increasing crop prices by 6%, while nitrate leaching declines by about 10%. Simulated nitrate export to the Gulf of Mexico decreases by 8%, ultimately shrinking the average midsummer area of the Gulf of Mexico hypoxic area by 3% and hypoxic volume by 4%. We also consider the additional benefits of restored wetlands to mitigate nitrogen loading to reduce hypoxia in the Gulf of Mexico and find a targeted wetland restoration scenario approximately doubles the effect of a low to moderate social cost of carbon. Wetland restoration alone exhibited spillover effects that increased nitrate leaching in other parts of the basin which were mitigated with the inclusion of the carbon policy. We conclude that a national climate policy aimed at reducing greenhouse gas emissions in the United States would have important water quality cobenefits. 

Abstract. This paper describes the University of New Hampshire Water Balance Model, WBM, a process-based gridded global hydrologic model that simulates the land surface components of the global water cycle and includes water extraction for use in agriculture and domestic sectors. The WBMwas first published in 1989; here, we describe the first fully open-sourceWBM version (v.1.0.0). Earlier descriptions of WBM methods provide the foundation for the most recent model version that is detailed here. We present an overview of themodel functionality, utility, and evaluation of simulated global riverdischarge and irrigation water use. This new version adds a novel suite ofwater source tracking modules that enable the analysis of flow-path histories on water supply. A key feature of WBM v.1.0.0 is the ability to identify the partitioning of sources for each stock or flux within the model. Three different categories of tracking are available: (1) primary inputs of water to the surface of the terrestrial hydrologic cycle (liquid precipitation, snowmelt, glacier melt, and unsustainable groundwater); (2) water that has been extracted for human use and returned to the terrestrial hydrologic system; and (3) runoff originating from user-defined spatial land units. Such component tracking provides a more fully transparent model in that users can identify the underlying mechanisms generating the simulated behavior. We find that WBM v.1.0.0 simulates global river discharge and irrigation water withdrawals well, even with default parameter settings, and for the first time, we are able to show how the simulation arrives at these fluxes by using the novel tracking functions.