Browsing by Subject "Nitrate"
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Item Anthropogenic impacts on recharge processes and water quality in basin aquifers of the desert Southwest : a coupled field observation and modeling study(2014-05) Robertson, Wendy Marie; Sharp, John Malcolm, Jr., 1944-The development of natural grass/scrubland for agricultural use within the Trans-Pecos basins has altered recharge mechanisms and raised questions about groundwater sustainability. Past efforts focused on recharge in arid basin systems used three main assumptions: there is minimal modern recharge, no widespread recharge on basin floors, and no recharge from anthropogenic sources. However, in the Trans-Pecos, nitrate (NO₃-) concentrations have increased in basin groundwater (up by 3-4 mg/l as NO₃- in 40 yrs), refuting the “classic” model and posing water quality risks. Grazing and irrigated agriculture have impacted basin hydrology by altering vegetation regime and the magnitude and spatial distribution of infiltration. This has increased recharge, Cl⁻, and mobile N flux to basin groundwater. A series of spatially-distributed net infiltration models were used to estimate potential recharge from natural and anthropogenic sources. Between 7-20% of potential recharge results from widespread recharge on the basin floors. Additionally, from 1960-2000, irrigation return flow may have contributed 3.0 × 10⁷ - 6.3 × 10⁷ m³ of recharge. These results are supported by field observations. Cores collected beneath agricultural land document changes in water content and pore water chemistry that imply increased downward flux of moisture and solute, and NO₃- and Cl- inventories beneath irrigated land are distinct in amount and profile from those in natural areas. There are significant implications for sustainability based upon the trends in groundwater NO₃- concentrations, core results, and net infiltration models: more recharge may enter the basins than previously estimated and there is a potential long-term concern for water quality. Due to thick unsaturated zones in the basins, long travel times are anticipated. It is unknown if NO3- and Cl⁻ flux has peaked or if effects will continue for years to come. Further study should be undertaken to examine anthropogenic impacts on basin water quality. Additionally, these impacts may occur in similar systems globally and there is considerable evidence for the re-evaluation of the validity of the “classic” model of recharge in arid basin systems. Future studies and management plans should incorporate potential impacts of changes in vegetation and land use on recharge processes and water budgets in arid basins.Item The energy-water nexus : an examination of the water quality impacts of biofuels(2010-05) Twomey, Kelly Marie; Webber, Michael E., 1971-; Lawler, Desmond F.Water and energy share an important relationship since it takes water to produce energy, and likewise, energy to pump, treat, and distribute water. This thesis explores the energy-water nexus in regards to electricity and transportation fuel production, as well as water treatment. It investigates how the Energy Independence and Security Act of 2007 might affect this interrelationship in the future since increases in corn cultivation for biofuels production are likely to lead to higher nitrate concentrations in US water reservoirs, which could trigger the requirement for additional energy consumption for drinking water treatment. The analysis indicates that advanced drinking water treatment might require an additional 2360 million kWh annually to treat drinking water currently exceeding the Environmental Protection Agency’s maximum contaminant level (MCL) limit of 10 mg per liter of nitrate-nitrogen. This is a 2100% increase in energy consumption for advanced water treatment to meet this MCL in comparison with surface water treatment alone. Although results indicate that most large surface and groundwater drinking water resources are not likely to exceed safe drinking water standards due to the expansion of corn-starch based ethanol production, smaller water reservoirs in agricultural regions are susceptible to nitrate contamination in the future. Consequently, these sources might require energy-intensive drinking water treatment to reduce nitrate levels below 10 mg per liter of nitrate-nitrogen. Based on these results, I conclude that projected increases in nitrate contamination in water may impact the energy consumed in the water treatment sector, because of the convergence of several related trends: (1) increasing cornstarch-based ethanol production, (2) increasing nutrient loading in surface water and groundwater resources as a consequence of increased corn-based ethanol production, (3) additional drinking water sources that exceed the MCL for nitrate, and (4) potentially more stringent drinking water standards for nitrate.Item Modeling autohydrogenotrophic treatment of perchlorate-contaminated water in the presence of nitrate(2009-08) London, Mara Rachel; Katz, Lynn Ellen; Speitel, Gerald E.Perchlorate contamination is widespread. Perchlorate, a water contaminant, disrupts iodide uptake to the thyroid, inhibiting growth and mental development. Recent studies have demonstrated autohydrogenotrophic perchlorate reduction to chloride. Hydrogen gas can be produced in-situ via the corrosion of zero-valent iron (ZVI), thereby avoiding problems related to the low aqueous solubility of hydrogen gas. The presence of nitrate has been shown inhibit autohydrogenotrophic perchlorate reduction. However, no studies have modeled the effects of nitrate on autohydrogenotrophic perchlorate biokinetics or developed a model to function as a design tool to predict long-term performance of ZVI/biotic perchlorate treatment systems in the presence of nitrate. Batch experiments demonstrated the presence of nitrate significantly inhibited perchlorate degradation by an autohydrogenotrophic microbial consortium. However, the consortium was capable of significant perchlorate reduction while the bulk of the nitrate was still present. A modified competitive inhibition model successfully predicted autohydrogenotrophic perchlorate degradation in the presence of nitrate. The model describes perchlorate degradation as a function of the biomass, perchlorate, hydrogen, and nitrate concentrations, as well as the single-component perchlorate, hydrogen, and nitrate half-saturation coefficients and perchlorate maximum substrate utilization rate. To obtain the single-component parameters, a series of batch experiments were performed under perchlorate-, nitrate-, and hydrogen-limiting conditions. The single-component biokinetic parameters and model predictions indicate the consortium could treat perchlorate-contaminated water with concentrations in the low hundreds of μg/L and in states with perchlorate treatment goals in the low μg/L range. The consortium biokinetic parameters and modified competitive inhibition model were used in the development of an AQUASIM based biofilm model. The model also integrated physical parameters, ZVI hydrogen production, and abiotic nitrate reduction. The model was calibrated using the long-term performance results of a laboratory-scale ZVI/biotic column. Both laboratory and modeling results showed when the column becomes hydrogen-limited, the presence of nitrate decreases perchlorate removal efficiency. Full-scale simulations demonstrated the model could prove useful as a predictive design tool. Simulations suggest that a permeable reactive barrier that includes 10% ZVI and additional media capable of pH buffering could remove typical contaminated ground water concentrations of perchlorate in the presence of typical oxygen and nitrate concentrations.Item Seasonal dynamics of organic matter and inorganic nitrogen in surface waters of Alaskan Arctic streams and rivers(2015-12) Khosh, Matthew Solomon; McClelland, James W.; Dunton, Kenneth H; Liu, Zhanfei; Shank, Gerald C; Townsend-Small, AmyClimate-linked changes in hydrology and biogeochemical processes within Arctic watersheds are likely already affecting fluvial export of waterborne materials, including organic matter (OM) and dissolved inorganic nitrogen (DIN). Our understanding of Arctic watershed OM and DIN export response to climate change is hampered by a lack of contemporary baselines, as well as a dearth of seasonally comprehensive studies. This work focuses on characterizing OM and DIN concentrations and sources in six streams/rivers on the North Slope of Alaska during the entirety of the hydrologic year (May through October) in 2009 and 2010. The highest OM concentrations occurred during spring snowmelt, with results indicating that terrestrial vegetation leachates are the major source of dissolved OM, while particulate OM originates from a degraded soil source. Over the hydrologic year, soils became a progressively increasing source of dissolved OM, while autochthonous production made up a sizeable proportion of particulate OM during base flow conditions. DIN concentrations were low throughout the spring and summer and increased markedly during the late summer and fall. Our findings suggest that penetration of water into thawed mineral soils, and a reduction in nitrogen assimilation relative to remineralization, may increase DIN export from Arctic watersheds during the late summer and fall. Although recent studies of Arctic rivers have emphasized the importance of the spring thaw period on OM export, our understanding of the mechanisms that control water chemistry observations during this time are still lacking. Experimental leaching results, from experiments conducted in 2014, suggest that aboveground plant biomass is a major source of dissolved OM in Arctic catchments during the spring, and that the timing of freezing and drying conditions during the fall may impact dissolved OM leaching dynamics on that same material the following snowmelt. Improved knowledge of OM and DIN temporal trends and the mechanisms that control seasonal concentrations is essential for understanding export dynamics of these water constituents in Arctic river systems. Perhaps more importantly, increased understanding of the seasonal controls on OM and DIN export in Arctic rivers is critical for predicting how these systems will respond under future climate change scenarios.Item Synthesis of palladium-gold alloy nanoparticle catalysts for the reduction of nitrite in water(2016-05-06) Seraj, Sarah; Werth, Charles J.; Humphrey, Simon M.Hydrogenation using palladium-based (Pd-based) catalysts has emerged as a promising treatment method for nitrate in drinking water. However, low catalytic activity and longevity can be a barrier to widespread adoption over conventional treatment methods. Controlling catalyst structure at the molecular scale is one approach to improving catalytic activity and longevity. Intermetallic palladium-gold nanoparticle (PdAu NP) alloy catalysts of varying composition were synthesized for nitrite reduction using a polyol reduction method and microwave-assisted heating. The average size of PdAu NPs was 4.1 ± 2.2 nm. Enhanced nitrite reduction has been previously observed for Pd combined with Au in a core-shell NP structure, but has not been studied for intermetallic PdAu alloy NPs. Moreover, the mechanism by which Au enhances Pd-catalyzed nitrite reduction is not well understood. The PdAu NPs were loaded into an amorphous silica support and evaluated for nitrite reduction in a batch reactor. Reaction followed pseudo first-order kinetics for greater than 80% of conversion. Catalyst activity showed volcano-like behavior with varying composition .... All PdAu alloys were significantly more active for nitrite reduction compared to pure Pd NPs, despite Au being catalytically inactive for hydrogenation. Sulfide fouling and catalyst longevity studies were conducted. The presence of Au in the catalyst structure did not appear to enhance resistance to sulfide fouling. Moreover, catalyst activity was reduced upon repeated cycles of nitrite reduction. Further investigation is required to understand the mechanism for catalyst deactivation.