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Headwaters may be small relative to other aquatic ecosystems, but they are neither simple nor static environments. Heterogeneous stream corridors constitute the majority of river network length and regulate cycling of carbon and oxygen as they expand and contract their connections across the landscape. Though headwater streams integrate many biogeochemical signals from the watersheds they drain and provide important ecosystem services, their diverse habitats and dynamic changes in wet length have been under- examined compared to dendritic, perennial streams. This oversight complicates efforts to identify biogeochemical patterns at larger scales. This dissertation sets out to expand our knowledge of stream biogeochemical responses to variable connections both within the channel and the wider stream corridor. First, I investigated how the presence and arrangement of different habitat patches in the stream corridor affected overall emissions of carbon dioxide (CO2) and methane (CH4) from sub-watersheds of a forested mountain stream network. To do this I measured concentration and flux of both gasses along and around 4 streams, including dry reaches and adjacent vernal pools as well as flowing water. I found that emissions were highly variable over space and time; in particular, the presence of a vernal pool enhanced total carbon emissions from the stream corridor. Next, to quantify carbon cycling and export from a non-perennial headwater stream, I monitored concentrations of CO2 and dissolved organic carbon (DOC) at the stream outlet. I found that CO2 concentration had a negative relationship with stream discharge, and that exports of both CO2 and DOC were driven by storms reconnecting isolated surface water reaches. I also found that carbon biogeochemistry of intermediate flow states were unique from driest and highest-flow conditions. Finally, to explore how isolated pools in the stream channel respond to flow decrease and cessation, I measured dissolved oxygen (DO) as well as CO2 and CH4 from persistent pools of two non- perennial streams throughout an unusually dry summer and fall. I found that hypoxia was common in all isolated pools, but swings in DO were not consistent between pools even of the same stream. In using diel changes in DO to estimate metabolism, I also found that ecosystem respiration varied by stream, but gross primary production was more driven by stream surface water connectivity. Climate change is inducing many new patterns in stream hydrology with critical implications for biogeochemical activity, from reducing durations of connectivity to causing stronger storms. Improving our understanding of how surface water and landscape connectivity both influence the movement of carbon within and through streams is essential to resolving questions about the contributions of freshwaters to the global carbon cycle. / Doctor of Philosophy / Headwater streams may seem inconsequential to larger ecosystem processes due to their small size. However, the majority of a river's network length, or the total length of all the streams and rivers from spring to ocean, is made up of headwater streams. The widespread presence of headwater streams over all types of land, along with the unique layout of different aquatic habitats near streams and the fact that small streams often grow and shrink in length, mean that studying headwaters can tell us many things about how energy moves through ecosystems. This dissertation explores how we can use changing headwater connectivity to understand how carbon moves through ecosystems. Connectivity in aquatic science refers to how water can move through space in ways that rocks and trees and even many animals cannot. This idea is useful because water carries things around as it moves, and its presence or absence enables reactions that are essential for the cycling of energy and nutrients. For instance, when water moves from high ground to low ground, it navigates through soil and holes in the ground; it may get slowed down at flat spots where little pools form. I measured emissions of carbon dioxide and methane from streams as well as soils, holes, and pools near mountain streams to try to understand how the path water takes influences how much carbon dioxide and methane escapes into the air. My measurements were surprisingly different depending on where and when I took them. I found that if a seasonal pond is connected to a stream channel, the stream will emit more greenhouse gasses than if the pond goes dry. Connectivity can also describe if water moves continuously along a stream, or if the stream goes dry in places and is then disconnected from different parts of itself. I asked how a stream becoming disconnected affected carbon dioxide emissions as well as the movement of dissolved organic carbon, a food source for microorganisms. I found that the less water moving through the stream channel, the higher carbon dioxide concentrations were. I also found that storms move both carbon dioxide and dissolved organic carbon out of streams quickly, even if the stream had been disconnected. Finally, I investigated the water that is left when streams disconnect. I measured dissolved oxygen, carbon dioxide, and methane in isolated pools of two disconnected streams. By tracking how microbes and algae consume and produce oxygen when a stream is not flowing, I can understand how these lifeforms adapt. I found that isolated pools frequently have very low levels of dissolved oxygen. This means that microorganisms in the pools have to use special ways of getting energy, which in turn affects how different forms of carbon move through the stream ecosystems. Headwater stream ecosystems are very sensitive to small changes in flow and precipitation; however, climate change means that streams are going dry more often than they used to. My findings contribute to our understanding of how changes in stream connectivity have many biological effects that are important for water quality and ecosystem health.

Deep row incorporation (DRI) is a biosolids recycling method that is especially appropriate for reclaiming disturbed land because of the extremely high application rates used. Nutrient additions in excess of the vegetation requirements, especially in coarse-textured soils, can potentially impair water quality. Increasing C and N additions with biosolids DRI can also generate emissions of greenhouse gases N₂O and CH₄ and decrease the value of C sequestration. Objectives of this research were: (i) compare the effects of DRI biosolids type and rate and annual conventional fertilizer application on N and P leaching losses; (ii) determine the effects of aging on the N, C and P dynamics in the DRI biosolids seams; (iii) compare the effects of biosolids type and conventional N fertilization on N₂O, CH₄ and CO₂ emissions; and (iv) compare the effects of DRI biosolids and conventional N fertilization on hybrid poplar biomass dynamics, C, N and P sequestration. The following eight treatments were established to achieve objectives (i) and (iv): 0 (control), 167, 337, 504 kg N ha⁻¹ yr⁻¹ as conventional fertilizer; 213 and 426 Mg ha⁻¹ anaerobically digested (AD) and 328 and 656 Mg ha⁻¹ lime stabilized (LS) biosolids applied in trenches. The amount of N lost from the DRI biosolids was 261–803 kg N ha⁻¹, while the fertilizer treatments were not different from 0 kg N ha⁻¹ yr⁻¹ control. Orthophosphate and TKP leached in negligible amounts. Deep row biosolids incorporation did not pose P leaching risks but did result in high N leaching below the biosolids seams. Aboveground biomass production in the biosolids treatments was not different from the control treatment and ranged from 2.1±0.3 to 4.0±0.5 kg tree⁻¹. The fertilizer treatments produced significantly less biomass than the control and the biosolids treatments. Hybrid poplars sequestered up to 3.20±0.54 Mg C ha⁻¹, 71±12 kg N ha⁻¹, and 11.0±1.8 kg P ha⁻¹. The planting density capable of the N uptake in order to avoid N leaching was estimated at 3912 to 11363 trees ha⁻¹. Our results suggest increased hybrid poplar planting density and decreased application rates of DRI biosolids may decrease the risk of groundwater contamination with N. Three treatments were compared to address objective (ii): 426 Mg ha⁻¹ AD and 656 Mg ha⁻¹ LS biosolids. Organic C losses were 81 Mg ha⁻¹ and 33 Mg ha⁻¹ for LS and AD biosolids, respectively. Total N lost over the course of two years was 15.2 Mg ha⁻¹ and 10.9 Mg ha⁻¹ for LS and AD biosolids, respectively, which was roughly 50% of the N applied. No significant losses of P were detected. Most of the P was Al- and Fe-bound in the AD biosolids and Ca-bound in the LS biosolids. Our results indicated that recommended rates of DRI biosolids in coarse textured soils should be based on crop N requirements and N mineralization considerations, and P mobility from biosolids of the type used should not pose a water quality risk. Four treatments were compared to address objective (iii): 426 Mg ha⁻¹ AD and 656 Mg ha⁻¹ LS biosolids; 0 (control) and 504 kg N ha⁻¹ y⁻¹ as conventional fertilizer. Contributions from CH₄ and CO₂ emissions to the radiative forcing were very small compared to N₂O. More N₂O was produced in the DRI biosolids treatments than in the conventional fertilizer treatments, and N₂O production was higher in AD than in LS. Expressed as global warming potentials, N₂O emissions from AD (101.5 Mg C ha⁻¹) were 4.6 times higher than from LS and 14.5-16.1 times higher than from the fertilizer treatments. High N₂O emissions from deep row incorporated biosolids reduce the C sequestration benefits of the DRI method. / Ph. D.

Increased floodplain and wetland restoration activity has raised concerns about potential impacts on the release of greenhouse gases (GHGs) to the atmosphere due to restored connectivity between aquatic and terrestrial ecosystems. Research has shown GHG fluxes from hydrologically active landscapes such as floodplains and wetlands vary spatially and temporally in response to primary controls including soil moisture, soil temperature, and available nutrients. In this study, we performed a semimonthly sampling campaign measuring GHG (CO2, CH4, and N2O) fluxes from six locations within a third-order stream floodplain. Site locations were based on dominant landscape positions and hydrologic activity along a topographic gradient including a constructed inset floodplain at the stream margin, the natural levee, an active slough, the general vegetated floodplain, a convergence zone fed by groundwater, and the upland area. Flux measurements were compared to abiotic controls on GHG production to determine the most significant factors affecting GHG flux from the floodplain. We found correlations between CO2 flux and soil temperature, organic matter content, and soil moisture, CH4 flux and pH, bulk density, inundation period length, soil temperature, and organic matter content. But minimal correlations between N2O flux and the measured variables. Spatially, our results demonstrate that constructed inset floodplains have higher global warming potential in the form of CH4 than any other site and for all other GHGs, potentially offsetting the positive benefits incurred by enhanced connectivity. However, at the reach scale, total CO2 flux from the soil remains the greater influence on climate since the area covered by these inset floodplains is comparatively much smaller than the rest of the floodplain. / Master of Science

Food waste is a desirable feedstock for anaerobic digestion because it is high in moisture and is an easily degradable material. However, mono-digestion of food waste often fails due to the accumulation of volatile fatty acids. Supplementing trace elements is one strategy to combat this issue. This study examined the effect of supplementing trace elements (iron, nickel, selenium, molybdenum, magnesium, zinc, calcium, copper, manganese, cobalt) on the methane yield and organic waste destruction of anaerobically digested food waste. Methane yield of food waste with and without the inorganic salt trace element was determined by the gas density-based biomethane potential method at mesophilic (37°C) conditions over 30 days. The three treatments were inoculum only, food waste and inoculum, and food waste and inoculum with an added trace element solution. There was no significant difference between treatments in terms of waste stabilization (percent volatile solids, total solids, and total chemical oxygen demand reduction) between treatments. The average cumulative biogas produced was 41% higher, and the average total cumulative methane produced was 23% higher in the treatment with the trace element supplement. Mean methane yield was not different (p > 0.05) between treatments over the 30 days, and there was no difference (p > 0.05) in biomethane potential between treatments. In addition, greenhouse gas reduction potential was estimated from food waste streams in Montgomery, VA using anaerobic digestion. The purpose of this work was to (1) estimate the total mass of food waste produced in Montgomery, VA in a year, (2) use the results from the biomethane potential analyses to inform the sizing of a theoretical community digester in Montgomery, VA, and (3) estimate the greenhouse gas reduction potential of anaerobically digesting the food waste instead of sending it to landfill. Greenhouse gas reduction was calculated using the Climate Action Reserve Organic Waste Digestion Project Protocol guidelines. The greenhouse gas reduction potential was estimated as 6,532 tonnes of carbon dioxide equivalent per year (tCO2e/year), with approximately 693 m3 methane produced per day. In one year, the digester would generate an estimated 7370 kWh of energy which has the potential to power 149 homes for a year in Montgomery, VA. In addition, 4130 tonnes/year of composted digestate would be available as fertilizer for surrounding farms. / Master of Science / Currently, about one-third of the entire U.S. food supply is lost or wasted. A large portion of that food waste is sent to landfills, where it produces methane, a greenhouse gas. Instead, food waste can be broken down to produce biogas during anaerobic digestion. Anaerobic digestion is a process in which microorganisms break down organic materials in the absence of oxygen to produce biogas and digestate, a material used as a soil amendment or fertilizer. However, anaerobically digesting food waste often leads to process instability and failure due to a buildup of undesirable intermediates. Microorganisms in anaerobic digestion require certain trace elements (i.e., iron, copper) that food waste often lacks; therefore, supplementing key trace elements may improve the anaerobic digestion of food waste. This research aimed to assess the effect of supplementing key trace elements (iron, copper, zinc, calcium, magnesium, nickel, manganese, selenium, molybdenum, cobalt) on organic matter degradation and methane yield. Methane yield of food waste with and without the inorganic salt trace element was determined by the gas density-based biomethane potential method at mesophilic (37°C) conditions over 30 days. The average cumulative biogas produced was 41% higher, and the average total cumulative methane produced was 23% higher in the bottles containing a trace element supplement. No significant difference was seen in the two groups when comparing organic matter degradation. These results demonstrate that supplementing trace elements can improve biogas and methane production. Greenhouse gas reductions from anaerobically digesting food waste instead of sending it to landfills were determined for Montgomery, VA. The results from the biomethane potential test informed the design of a theoretical community digester. Greenhouse gas reduction was calculated using the Climate Action Reserve Organic Waste Digestion Project Protocol equations. The greenhouse gas reduction was determined as 6,532 tonnes of carbon dioxide equivalent per year (tCO2e/year). The digester would produce approximately 693 m3 methane/day, which has the potential to power 149 homes for a year in Montgomery, VA. In addition, 4130 tonnes/year of compost would be produced and available as a fertilizer for surrounding farms.