The controls of watershed nutrient export

Anthropogenic nitrogen (N) loading has increased considerably in recent times, yet only a small proportion is generally exported to the coast from most watersheds. This dissertation addresses some of the factors controlling N export from watersheds. The focus is on (1) how N export and N retention change with increased urbanization, and (2) how river networks modify N that is loaded to them. Urbanization is a major perturbation of the land surface. Chapter 1 uses a budget approach to assess how N retention changes with increased urbanization in small headwater catchments in northeastern Massachusetts, USA. Water runoff, N loading, and N exports were higher in an urban compared to a forested site. N exports increased at a faster rate than N loading, indicating that the capacity of urban catchments to retain nutrients has declined. Impervious surfaces are likely a major factor leading to this decline. Aquatic systems can store or denitrify a large amount of N, and can therefore potentially buffer increased N loading from terrestrial systems (non-point sources) and point sources. Chapter 2 uses a modeling approach to assess the role of river networks at the global scale. The strength of aquatic N removal varied considerably by watershed, depending on the spatial distribution of N loading, hydraulic characteristics, and biological activity. The representation of biological activity strongly influenced predicted N removal of aquatic systems, pointing out the need to better understand biological controls in different regions of the world. A great deal of attention has recently been given to the role of river networks in modifying nutrient exports. Chapter 3 is an exploration of the biological and hydrological controls of nutrient removal at the scale of river networks. In particular, the role of stream size and nutrient concentrations are emphasized. The analysis suggests that river network models should clearly separate the biological and hydrological parameters to (1) facilitate understanding of model behavior, (2) facilitate comparability with field measurements, (3) improve the ability to apply/test models across temporal and spatial domains, and (4) improve the ability to explore the relative influences hydrological and biological controls of river network nutrient removal

An index to characterize the spatial distribution of land use within watersheds and implications for river network nutrient removal and export

The spatial distribution of land use and associated nutrient inputs may influence the efficacy of in-stream nutrient removal; however, the effect of source location on N removal and watershed N export has not been quantified. We present the skewness index, a metric to quantify the spatial distribution of land use within watersheds. Using this index and a river network nitrogen removal model, we quantified the effect of varying the location of developed land use within two watersheds on nutrient removal and export. The quantity and location of developed land use as well as runoff affected nitrogen removal and export. Because river network nitrogen removal is bypassed when sources are skewed toward the watershed mouth, varying the location of land use alone can double aquatic nitrogen removal. Nutrient sources skewed toward the distant headwaters maximized in-stream removal which in turn can reduce watershed export

History of nutrient inputs to the northeastern United States, 1930–2000

Humans have dramatically altered nutrient cycles at local to global scales. We examined changes in anthropogenic nutrient inputs to the northeastern United States (NE) from 1930 to 2000. We created a comprehensive time series of anthropogenic N and P inputs to 437 counties in the NE at 5 year intervals. Inputs included atmospheric N deposition, biological N2 fixation, fertilizer, detergent P, livestock feed, and human food. Exports included exports of feed and food and volatilization of ammonia. N inputs to the NE increased throughout the study period, primarily due to increases in atmospheric deposition and fertilizer. P inputs increased until 1970 and then declined due to decreased fertilizer and detergent inputs. Livestock consistently consumed the majority of nutrient inputs over time and space. The area of crop agriculture declined during the study period but consumed more nutrients as fertilizer. We found that stoichiometry (N:P) of inputs and absolute amounts of N matched nutritional needs (livestock, humans, crops) when atmospheric components (N deposition, N2 fixation) were not included. Differences between N and P led to major changes in N:P stoichiometry over time, consistent with global trends. N:P decreased from 1930 to 1970 due to increased inputs of P, and increased from 1970 to 2000 due to increased N deposition and fertilizer and decreases in P fertilizer and detergent use. We found that nutrient use is a dynamic product of social, economic, political, and environmental interactions. Therefore, future nutrient management must take into account these factors to design successful and effective nutrient reduction measures

Longer thaw seasons increase nitrogen availability for leaching during fall in tundra soils

Climate change has resulted in warmer soil temperatures, earlier spring thaw and later fall freeze-up, resulting in warmer soil temperatures and thawing of permafrost in tundra regions. While these changes in temperature metrics tend to lengthen the growing season for plants, light levels, especially in the fall, will continue to limit plant growth and nutrient uptake. We conducted a laboratory experiment using intact soil cores with and without vegetation from a tundra peatland to measure the effects of late freeze and early spring thaw on carbon dioxide (CO2) exchange, methane (CH4) emissions, dissolved organic carbon (DOC) and nitrogen (N) leaching from soils. We compared soil C exchange and N production with a 30 day longer seasonal thaw during a simulated annual cycle from spring thaw through freeze-up and thaw. Across all cores, fall N leaching accounted for ~33% of total annual N loss despite significant increases in microbial biomass during this period. Nitrate $({{{\rm{NO}}}_{3}}^{-})$ leaching was highest during the fall (5.33 ± 1.45 mg N m−2 d−1) following plant senescence and lowest during the summer (0.43 ± 0.22 mg N m−2 d−1). In the late freeze and early thaw treatment, we found 25% higher total annual ecosystem respiration but no significant change in CH4 emissions or DOC loss due to high variability among samples. The late freeze period magnified N leaching and likely was derived from root turnover and microbial mineralization of soil organic matter coupled with little demand from plants or microbes. Large N leaching during the fall will affect N cycling in low-lying areas and streams and may alter terrestrial and aquatic ecosystem nitrogen budgets in the arctic

Controls on dissolved organic carbon quantity and chemical character in temperate rivers of North America

Understanding the processes controlling the transfer and chemical composition of dissolved organic carbon (DOC) in freshwater systems is crucial to understanding the carbon cycle and the effects of DOC on water quality. Previous studies have identified watershed‐scale controls on bulk DOC flux and concentration among small basins but fewer studies have explored controls among large basins or simultaneously considered the chemical composition of DOC. Because the chemical character of DOC drives riverine biogeochemical processes such as metabolism and photodegradation, accounting for chemical character in watershed‐scale studies will improve the way bulk DOC variability in rivers is interpreted. We analyzed DOC quantity and chemical character near the mouths of 17 large North American rivers, primarily between 2008 and 2010, and identified watershed characteristics that controlled variability. We quantified DOC chemical character using both specific ultraviolet absorbance at 254 nm (SUVA254) and XAD‐resin fractionation. Mean DOC concentration ranged from 2.1 to 47 mg C L−1 and mean SUVA254 ranged from 1.3 to 4.7 L mg C−1 m−1. We found a significant positive correlation between basin wetland cover and both bulk DOC concentration (R2 = 0.78; p \u3c 0.0001) and SUVA254 (R2 = 0.91; p \u3c 0.0001), while other land use characteristics were not correlated. The strong wetland relationship with bulk DOC concentration is similar to that found by others in small headwater catchments. However, two watersheds with extremely long surface water residence times, the Colorado and St. Lawrence, diverged from this wetland relationship. These results suggest that the role of riverine processes in altering the terrestrial DOC signal at the annual scale was minimal except in river systems with long surface water residence times. However, synoptic DOC sampling of both quantity and character throughout river networks will be needed to more rigorously test this finding. The inclusion of DOC chemical character will be vital to achieving a more complete understanding of bulk DOC dynamics in large river systems

Riverine ecosystem services and the thermoelectric sector: strategic issues facing the Northeastern United States

Major strategic issues facing the global thermoelectric sector include environmental regulation, climate change and increasing electricity demand. We have addressed such issues by modeling thermoelectric generation in the Northeastern United States that is reliant on cooling under five sensitivity tests to evaluate losses/gains in power production, thermal pollution and suitable aquatic habitat, comparing the contemporary baseline (2000–2010) with potential future states. Integral to the analysis, we developed a methodology to quantify river water availability for cooling, which we define as an ecosystem service. Projected climate conditions reduce river water available for efficient power plant operations and the river\u27s capacity to absorb waste heat, causing a loss of regional thermoelectric generation (RTG) (2.5%) in some summers that, compared to the contemporary baseline, is equal to the summertime electricity consumption of 1.3 million Northeastern US homes. Vulnerabilities to warm temperatures and thermal pollution can be alleviated through the use of more efficient natural gas (NG) power plants that have a reduced reliance on cooling water. Conversion of once-through (OT) to cooling tower (CT) systems and the Clean Water Act (CWA) temperature limit regulation, both of which reduce efficiencies at the single plant level, show potential to yield beneficial increases in RTG. This is achieved by obviating the need for large volumes of river water, thereby reducing plant-to-plant interferences through lowering the impact of upstream thermal pollution and preserving a minimum standard of cooling water. The results and methodology framework presented here, which can be extrapolated to other regional assessments with contrasting climates and thermoelectric profiles, can identify opportunities and support decision-making to achieve more efficient energy systems and riverine ecosystem protection

The biogeochemical influence of nitrate, dissolved oxygen, and dissolved organic carbon on stream nitrate uptake

Streams are potential hotspots for retention and removal of NO3−, and understanding the mechanisms that enhance NO3− reactivity in stream systems is critical for predicting and preventing eutrophication. Both dissolved organic C (DOC) and dissolved O2 (DO) influence NO3− removal processes. Assessing the individual impacts of NO3−, DO, and DOC concentrations on stream NO3− removal is difficult because these factors covary and are coupled through the C and N cycles. We used an experimental approach to quantify the influences of NO3−, DOC, and DO on NO3− transport in headwater streams of the Ipswich and Parker River watersheds (Massachusetts, USA) with contrasting levels of DOC and DO. In a 1st set of experiments, we added NO3− to address how uptake kinetics differed between a low-DO/high-DOC stream (Cedar Swamp Creek) and a high-DO/low-DOC stream (Cart Creek). In a 2nd set of experiments, we manipulated, for the first time at the reach scale, both DO and DOC in a factorial experiment. DO was added to the low-DO stream by injecting O2 and was removed from the high-DO stream by adding sodium sulfite. DOC was added both alone and in combination with the DO manipulations. NO3− concentration was an important control of NO3− uptake velocity in our study streams, consistent with previous findings. The results of the DOC and DO manipulations suggested that DO determines whether a stream has net NO3− uptake or production and that the presence of DOC magnifies the DO response processes. Addition of DOC by itself did not lead to increased NO3− uptake. In addition, we observed organic matter priming effects, wherein the addition of labile organic matter resulted in accelerated metabolism of naturally occurring DOC in the water column. Priming effects have not been reported previously in stream systems. Results from our experiments suggest that NO3− uptake in streams might arise from complex interactions among DOC, DO, and NO3−, and ultimately, from the influence of DO on dominant stream processes

Horizontal cooling towers: riverine ecosystem services and the fate of thermoelectric heat in the contemporary Northeast US

The electricity sector is dependent on rivers to provide ecosystem services that help regulate excess heat, either through provision of water for evaporative cooling or by conveying, diluting and attenuating waste heat inputs. Reliance on these ecosystem services alters flow and temperature regimes, which impact fish habitat and other aquatic ecosystem services. We demonstrate the contemporary (2000–2010) dependence of the electricity sector on riverine ecosystem services and associated aquatic impacts in the Northeast US, a region with a high density of thermoelectric power plants. We quantify these dynamics using a spatially distributed hydrology and water temperature model (the framework for aquatic modeling in the Earth system), coupled with the thermoelectric power and thermal pollution model. We find that 28.4% of thermoelectric heat production is transferred to rivers, whereas 25.9% is directed to vertical cooling towers. Regionally, only 11.3% of heat transferred to rivers is dissipated to the atmosphere and the rest is delivered to coasts, in part due to the distribution of power plants within the river system. Impacts to the flow regime are minimal, while impacts to the thermal regime include increased river lengths of unsuitable habitats for fish with maximum thermal tolerances of 24.0, 29.0, and 34.0 ° C in segments downstream of plants by 0.6%, 9.8%, and 53.9%, respectively. Our analysis highlights the interactions among electricity production, cooling technologies, aquatic impacts, and ecosystem services, and can be used to assess the full costs and tradeoffs of electricity production at regional scales

Removal of terrestrial DOC in aquatic ecosystems of a temperate river network

Surface waters play a potentially important role in the global carbon balance. Dissolved organic carbon (DOC) fluxes are a major transfer of terrestrial carbon to river systems, and the fate of DOC in aquatic systems is poorly constrained. We used a unique combination of spatially distributed sampling of three DOC fractions throughout a river network and modeling to quantify the net removal of terrestrial DOC during a summer base flow period. We found that aquatic reactivity of terrestrial DOC leading to net loss is low, closer to conservative chloride than to reactive nitrogen. Net removal occurred mainly from the hydrophobic organic acid fraction, while hydrophilic and transphilic acids showed no net change, indicating that partitioning of bulk DOC into different fractions is critical for understanding terrestrial DOC removal. These findings suggest that river systems may have only a modest ability to alter the amounts of terrestrial DOC delivered to coastal zones

Spatial distribution of land type in regression models of pollutant loading

This paper proposes a method to improve landscape-pollution interaction regression models through the inclusion of a variable that describes the spatial distribution of a land type with respect to the pattern of runoff within a drainage catchment. The proposed index is used as an independent variable to enhance the strength, as quantified by R² values, of regression relationships between empirical observations of in-stream pollutant concentrations and land type by considering the spatial distribution of key land-type categories within the sample point’s drainage area. We present an index that adds a new dimension of explanatory power when used in conjunction with a variable describing the proportion of the land type. We demonstrate the usefulness of this index by exploring the relationship between nitrate ( - 3 NO ) and land type within 40 drainage sub-catchments in the Ipswich River watershed, Massachusetts. Nutrient loads associated with non-point source pollution paths are related to land type within the up-stream drainage catchments of sample sites. Past studies have focused on the quantity of particular land type within a sample point’s drainage catchment. Quantifying the spatial distribution of key land-type categories in terms of location on a runoff surface can improve our understanding of the relationship between sampled - 3 NO concentrations and land type. Regressions that employ the proportion of residential and agricultural land type within catchments provide a fair fit (R² = 0.67). However, we find that a regression adding a variable that indicates the spatial distribution of residential land improves the overall relationship between instream - 3 NO measurements and associated land types (R² = 0.712). We test the sensitivity of the results with respect to variations in the surface definition in order to determine the conditions under which the spatial index variable is useful