The repercussions of rapid climate-change are felt worldwide, but particularly in Arctic and Subarctic regions. Evidence of recent changes in water chemistry is being recorded in Arctic aquatic ecosystems, bringing further attention to contaminant dynamics in these environments. I assessed the role of dissolved organic matter (DOM) in controlling the bioavailability of mercury (Hg), a top priority among Arctic contaminants, to aquatic food webs using a bacterial bioreporter under oxic conditions. Experiments were performed under pseudo- and non-equilibrium conditions, in both defined media and water samples from tundra lakes with a large gradient in DOM. Inorganic HgII was considerably more bioavailable under non-equilibrium conditions than when DOM was absent or when HgII and DOM had reached pseudoequilibrium (24h). Under these enhanced uptake conditions, HgII bioavailability followed a bell shaped curve as DOM concentrations increased, both for defined media and field samples, suggesting that complexation kinetics and binding thresholds on DOM determine HgII bioavailability to methylating bacteria, and likely MeHg concentrations, the bioaccumulative neurotoxic form of Hg. Experiments also suggest that DOM may alter cell wall properties to facilitate the first steps toward HgII internalization via facilitated or active transport, and yet without altering overall cell wall permeability. While further research on ternary (HgII-cell-DOM) interaction is warranted, I propose a molecular shuttle model for DOM in facilitating bacterial HgII uptake, and the existence of a short-lived yet critical time window (<24h) during which DOM facilitates the entry of newly deposited HgII from the atmosphere into aquatic food webs.

Channing Lake Basin, located west and northwest of Channing, in the Texas Panhandle, is of substantial area and presumably includes lake beds of Pliocene and Pleistocene ages within the Rita Blanca Formation, a member of the Ogallala Group. The foci of this study were a micritic ooid layer and a directly overlying stromatolite layer, which crop out in a canyon approximately 10 kilometers west of Channing. Research was conducted primarily using petrographic and scanning electron microscopy. Significant conclusions include: organic matter was preserved in ooids as filaments and nanoscale spheroids, which served to capture ostracode carapaces within ~10% of micritic cortices; and stromatolites were deposited within an evolving alkaline lacustrine environment producing discernible zones. Potential significance includes improving the understanding the role of organic matter in calcium carbonate precipitation, which has plausible applications in medical, industrial, and academic realms.

Due to the flocculation process, suspended mud aggregates carried by rivers and streams can undergo changes in their size, shape, and settling velocity in response to environmental drivers such as turbulence, sediment concentration, organic matter (OM), and salinity. Some have assumed that salt is necessary for floc formation, and that mud, therefore, reaches the estuary unflocculated. Yet mud flocs exist in freshwater systems long before the estuarine zone, likely due to the presence of OM and ions in the water that facilitate binding and aggregation of mud particles. This research aimed to examine the flocculation state of mud over the fluvial as well as fluvial to marine transition (FtMT) zones of the Mississippi River basin and how salinity, or the ion concentration of water, and organic matter independently and together affect flocculation. Suspended mud was found to be mostly flocculated in the headwaters of the Mississippi River in southwest Virginia, USA. However, increasing the ion concentration of water samples to levels measured following winter storms changed the size distribution of suspended particles, led to more of the mud existing in large flocs, and resulted in an overall increase in average size by about 40%, thereby increasing the settling rate of the mud relative to the suspensions without salt. These results suggested that potential negative effects of road salts on mud deposition should be investigated further. Additional experiments were used to examine the flocculation of a natural mud sample with and without OM showed that the rate of floc growth and equilibrium size both increase with salinity regardless of the presence or absence of OM. However, the response of both to salinity was stronger when OM was present. In deionized water, natural sediment with OM was seen to produce large flocs. However, the size distribution of the suspension tended to be bimodal. With the addition of salt, increasing amounts of unflocculated material became bound within flocs, producing a more unimodal size distribution. Here, the enhancing effects of salt were noticeable at even 0.5 ppt, and increases in salinity past 3 to 5 ppt only marginally increased the floc growth rate and final size. A salinity-dependent model to account for changes in floc growth rate and equilibrium size was presented. Laboratory experiments on the sediment suspended in the lower reaches of the Mississippi River were used to provide further insight on the mud flocs behavior in the FtMT. Turbulence shear rate, a proxy for the river hydrodynamics, was found to be the most influential factor in mud floc size. While artificial increase in salinity by adding of salts did not lead to considerable increase in floc size, addition of water collected from the Gulf of Mexico enhanced the flocculation. These effects were speculated to originate from the biomatter composition of the Gulf water, particularly where the nutrient-rich Mississippi River water reaches the marine water. / Doctor of Philosophy / Rivers bring a substantial amount of mud to coastal regions. Where this mud deposits is important in shaping the coastal land and nutrient dynamics. Mud particles are different from sand and gravel in that they can form aggregates known as flocs that constantly change shape and size under different conditions. As they change size, they change how fast they sink, and this influences where they deposit. Due to their small size, mud particles are also considered a pollutant as they can clog up fish gills and destroy freshwater habitats. Findings of this dissertation showed that the roadway deicing salts that make their way to streams can enhance the aggregation of mud particles, causing them to sink faster. This can be harmful to the species that live on streambeds. While salts are known to enhance flocculation, there is ample evidence that flocs exist in rivers before reaching the sea. It is possible, therefore, that flocs in estuaries are due to biological matter acting as a glue to bind mud particles together and may not be influenced by salt. This dissertation looked at the effects of saltwater on mud flocculation when biological matter is present and when it is absent. Findings showed that salinity increased the size of mud flocs, even more so than when organic matter was absent. However, organic matter was needed for flocs to reach sizes often found in nature. An equation was also provided to aid in the prediction of floc size under different salinities. Observations on the lower Mississippi River flocs showed that the turbulence of water was the most influential factor in determining the size of flocs.

Insect pests are the most widespread disturbance in Canadian forests, but resulting impacts of forest defoliation on stream ecosystem functions are poorly understood. This study investigated the effects of a spruce budworm outbreak on water quality and the structure and function of microbial communities in streams of 12 catchments across a gradient of cumulative defoliation severity in the Gaspésie Peninsula, Québec, Canada. Bi-weekly stream habitat sampling was conducted spring to fall 2019-2021, with stream flow rates measured and water samples collected and analyzed for water chemistry parameters, nutrients, and dissolved organic matter (DOM) structure and quality. Algal communities were assessed at the same time by measuring in-situ biomass. Bacteria and fungi communities on leaf packs were assessed by incubating six leaf packs for five weeks (mid-August- late September) in one stream reach per watershed. Microbial community composition of leaf packs was determined using metabarcoding of 16S and ITS rRNA genes, and functions were examined using extracellular enzyme assays, leaf litter decomposition rates, and taxonomic functional assignments. This study determined that cumulative defoliation increased stream temperatures, flow rates, and SUVA (DOM aromaticity), but not nutrients. It increased algal biomass and altered microbial community composition, with a stronger influence on bacteria than fungi. The observed increases in SUVA and algal biomass corresponded with changes to bacteria carbon cycling functions, which indicated that microbes were preferentially selecting carbohydrates produced by algae rather than the aromatic compounds from increased terrestrial inputs. There were no changes to other bacteria or fungi functions and no changes to taxonomic or functional diversity. Overall, results indicate that forest pest outbreaks alter carbon inputs to streams and the structure and function of stream microbial communities associated with carbon cycling. / Thesis / Master of Science (MSc) / Terrestrial and aquatic landscapes are tightly linked, and forest disturbances can influence stream ecosystems. Insect pests defoliate millions of hectares of forests each year, but the resulting impacts on stream ecosystems are poorly understood. This study investigated the effects of a spruce budworm outbreak on water quality and microbial communities in streams in Gaspésie, QC, Canada. Microbial communities are critical to the functioning of stream ecosystems as they convert energy (e.g., carbon) into useable forms for other organisms. Results indicate that defoliation altered stream flow rates, temperatures, and carbon composition, as well as the microbial communities involved in carbon cycling processes. Carbon is essential to aquatic food webs and this improved understanding of how carbon flow is altered by a widespread forest disturbance can inform pest management decisions for spruce budworm outbreaks.

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Hydrologic and material dynamics of ephemeral rivers were investigated in the Namib Desert to assess how hydrologic regimes shape the physical habitat template of these river ecosystems. An analysis of long-term hydrologic records revealed that the variation in mean annual runoff and peak discharge were nearly four times higher than the global average, rendering the rivers among the most variable fluvial systems yet described. Further, a pronounced downstream hydrologic decay characterized all of the rivers. The high spatio-temporal variability in flow was reflected in patterns of material transport. Retention of woody debris increased downstream, in contrast to patterns typically reported from more mesic systems, largely attributable to hydrologic decay. Woody debris piles were the principal retentive obstacles and played an important role in channel dynamics. They were also key microhabitats for various organisms, forming "hotspots" of heterotrophic activity analogous to patterns reported from perennial streams. Large amounts of fine particulate and dissolved organic matter (FPOM and DOM) deposited in the lower reaches of the rivers serve to fuel this heterotrophic biota. As a result of the hydrologic decay, sediment concentration (both organic and inorganic) increased downstream and the lower reaches of these rivers acted as sinks for material exported from their catchments. FPOM and DOM concentrations were among the highest reported for any aquatic system, and, contrary to patterns reported from more mesic systems, FPOM dominated the total organic load transported in these rivers. Inorganic solute concentration also increased downstream, resulting in a downstream increase in soluble salt content in floodplain soils. Soils within the river's lower reaches served as effective long-term integrators of hydrologic variability. The mean extent of floods entering the lower river was defined by an alluviation zone, evident from the convexity exhibited in the lower section of the rivers' longitudinal profiles. A downstream increase in the proportion of silt within floodplain soils is associated with increased sediment deposition. Silt deposition had a positive influence on moisture availability, plant rooting, and habitat suitability for various organisms, including fungi and invertebrates. In addition, a strong positive correlation was observed between silt, organic matter, and macronutrients. Thus, the hydrologic control of transport and deposition patterns has important implications for the structure and function of ephemeral river ecosystems. Finally, an examination of the influence of elephants upon riverine vegetation highlighted the importance of these systems as isolated resource patches interspersed in an arid and hostile landscape. Further, it illustrated that flooding was a key ecological process and that hydrologic alterations would affect the fluvial ecosystem as well as the regional landscape they drain. / Ph. D.

Removal of organic matter is increasingly important to drinking water utilities and consumers. Organic matter is a significant precursor in the formation of disinfection by-products (DBPs). The maximum contaminant levels for (DBPs) are decreasing and more DBPs are believed carcinogenic. Traditional coagulation focuses on the removal of particulate matter and in the last decade soluble species have also been targeted with high coagulant doses. However, colloidal matter is smaller than particulate matter and therefore not easily removed by conventional drinking water treatment. This research focused on the conversion of soluble organic matter to colloids using relatively low doses of ferric sulfate coagulant and the subsequent removal of the colloids by filtration during drinking water treatment. The goal is to achieve enhanced removal of soluble organic matter with minimal chemical costs and residual formation. This study investigated the effects of pH, iron coagulant dose, turbidity, organic matter concentration, and temperature on colloid formation. Characterization of the colloidal organic matter was attempted using zeta potential and sizing analyses. Cationic low molecular weight, nonionic high molecular weight, and cationic medium molecular weight polymers were evaluated on their removal of colloidal organic matter. Colloidal organic matter formation was affected by changes in coagulation pH, coagulant dose, and organic matter concentration, whereas turbidity and temperature did not significantly impact colloid formation. Decreased coagulation pH caused increased organic carbon removal. As coagulant dose was increased, colloid formation initially increased to maximum and subsequently rapidly decreased. Colloid formation was increased as the organic matter concentration increased. Due to low sample signal, the colloids could not be characterized using zeta potential and sizing analyses. In addition, polymers were ineffective for aggregating colloidal organic matter when used as flocculant aids. / Master of Science

Understanding hydrologic controls on carbon accumulation and export within geographically isolated wetlands (GIW) has implications for the success of wetland restoration efforts intended to produce carbon sinks. However, little is known about how hydrologic connectivity along the aquatic-terrestrial interface in GIW catchments influences carbon dynamics, particularly regarding dissolved organic matter (DOM) transport and transformation. The organic matter (carbon) that accumulates in wetland soils may be released into water, generating DOM. DOM is mobile and reactive, making it influential to aquatic metabolism and water quality. To understand the role of different soil horizons as potential sources of DOM, extractable soil organic matter (ESOM) was measured in soil horizons collected from upland to wetland transects at four Delmarva Bay GIWs on the Delmarva Peninsula in the eastern United States. ESOM quantity and quality were analyzed to provide insights to organic matter sources and chemical characteristics. Findings demonstrated that ESOM in shallow organic horizons had increased aromaticity, higher molecular weight, and plant-like signatures. ESOM from deeper, mineral horizons had lower aromaticity, lower molecular weights, and protein-like signatures. Organic soil horizons had the largest quantities of ESOM, and ESOM decreased with increasing soil depth. ESOM quantities also generally decreased from the upland to the wetland, suggesting that continuous soil saturation leads to a decreased quantity of ESOM. Despite wetland soils having lower ESOM, these horizons are thicker and continuously hydrologically connected to wetland surface water, leading to wetland soils representing the largest potential source of DOM to the Delmarva Bay wetland system. Knowledge of which soil horizons are most biogeochemically significant for DOM transport in Delmarva and other GIW systems will become increasingly important as climate change is expected to alter the hydrologic connectivity of wetland soils to the surface water-groundwater continuum and as wetlands are more frequently designed for carbon sequestration. / Master of Science / Wetlands store carbon in their plant biomass and soils, which helps to mitigate the effects of climate change by keeping carbon out of the atmosphere. Carbon builds up in wetland soils because the continuously wet conditions slow down the microbial processes that would otherwise break down the organic matter (carbon) and release it to the atmosphere via greenhouse gas emissions. However, the organic matter that accumulates in wetland soils may be released into water, generating dissolved organic matter (DOM). This DOM has the potential to flow out of the wetland, providing a source of energy to aquatic organisms or impacting downstream water quality. Not all wetlands are continuously connected to other water bodies. Geographically Isolated Wetlands (GIW) are wetlands that you could walk all the way around and keep your feet dry. Despite lack of continuous surface water connections, GIWs may still influence downstream water quality via groundwater flow paths or seasonal surface water connections. This variable connectivity makes GIWs a unique setting to study carbon storage and fluxes in wetland soils. The potential for soil-derived DOM generation was studied by extracting organic matter from soils along a wet to dry gradient in Delmarva Bay GIWs. Shallow soils had the largest quantities of extractable soil organic matter (ESOM) and this organic matter is likely sourced from plant inputs to the soil. ESOM from deeper soils was more similar to the microbes that consume and alter the organic matter as it cycles deeper into the soil. Soils located in the wetland basin had less ESOM because continuous saturation depleted the pool of ESOM. Despite lower values of ESOM, wetland soils are very thick and continuously saturated, making these soils the largest potential contributor of soil-derived DOM to Delmarva Bay GIWs. This work furthers our understanding of how hydrology drives carbon cycling in GIWs and will inform wetland restoration efforts designed to create carbon sinks.

This research evaluated natural organic matter (NOM) dissolved-solid phase separation resulting from alum coagulation under the following sourcewater conditions: pH, initial NOM concentration, initial turbidity, and temperature. The solid phase was partitioned into two operationally defined size fractions; colloidal matter was defined as organic carbon (OC) retained by a 30 kilodalton ultrafiltration membrane, and particulate matter was defined as OC retained by a 1μm glass-fiber filter. Coagulation pH had a considerable impact on residual OC colloid formation, signified by more colloids formed as a function of alum dose at pH 6.8 as compared to pH 5.8. Initial NOM concentration strongly influenced the alum dose range over which OC colloid formation occurred and was found to be a proportional relationship. The presence of bentonite clay (used as the initial turbidity source) somewhat affected OC colloid formation by exerting some amount of coagulant demand, signified by decreasing OC colloid formation with increasing initial turbidity. Coagulation temperature had a considerable impact on particulate matter formation, as there was an increase in the dose at which particle formation first occurred at 4 ºC when compared to 25 ºC. Phase separation of OC from dissolved to colloidal matter was very similar at both 4 ºC and 25 ºC. The ability for low doses of polymers to replace a large portion of alum in order to further aggregate colloids during flocculation was unsuccessfully investigated. OC phase separation resulting from alum and iron sulfate coagulation was compared on a molar coagulant metal basis. The amount of residual OC associated with colloidal matter was similar, while the critical coagulant dose at which particulate matter formed was shifted to a much higher dose for iron. / Master of Science