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Quantifying Whole-Reach Denitrification in Arizona Streams

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Elevated nitrate (NO3-) concentration in streams and rivers has contributed to environmental problems such as downstream eutrophication and loss of biodiversity. Sycamore Creek in Arizona is nitrogen limited, but previous studies have demonstrated high potential for denitrification, a microbial process

Elevated nitrate (NO3-) concentration in streams and rivers has contributed to environmental problems such as downstream eutrophication and loss of biodiversity. Sycamore Creek in Arizona is nitrogen limited, but previous studies have demonstrated high potential for denitrification, a microbial process in which biologically active NO3- is reduced to relatively inert dinitrogen (N2) gas. Oak Creek is similarly nitrogen limited, but NO3- concentration in reaches surrounded by agriculture can be double that of other reaches. We employed a denitrification enzyme assay (DEA) to compare potential denitrification rate between differing land uses in Oak Creek and measured whole system N2 flux using a membrane inlet mass spectrometer to compare differences in actual denitrification rates at Sycamore and Oak Creek. We anticipated that NO3- would be an important limiting factor for denitrifiers; consequentially, agricultural land use reaches within Oak Creek would have the highest potential denitrification rate. We expected in situ denitrification rate to be higher in Oak Creek than Sycamore Creek due to elevated NO3- concentration, higher discharge, and larger streambed surface area. DEA results are forthcoming, but analysis of potassium chloride (KCl) extraction data showed that there were no significant differences between sites in sediment extractable NO3- on either a dry mass or organic mass basis. Whole-reach denitrification rate was inconclusive in Oak Creek, and though a significant positive flux in N2 from upstream to downstream was measured in Sycamore Creek, the denitrification rate was not significantly different from 0 after accounting for reaeration, suggesting that denitrification does not account for a significant portion of the NO3- uptake in Sycamore Creek. Future work is needed to address the specific factors limiting denitrification in this system.

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2018-05

Heterogeneous Catalysis for Organic Reactions

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This honors thesis is focused on two separate catalysis projects conducted under the mentorship of Dr. Javier Pérez-Ramírez at ETH Zürich. The first project explored ethylene oxychlorination over supported europium oxychloride catalysts. The second project investigated alkyne semihydrogenation over nickel

This honors thesis is focused on two separate catalysis projects conducted under the mentorship of Dr. Javier Pérez-Ramírez at ETH Zürich. The first project explored ethylene oxychlorination over supported europium oxychloride catalysts. The second project investigated alkyne semihydrogenation over nickel phosphide catalysts. This work is the subject of a publication of which I am a co-author, as cited below.

Project 1 Abstract: Ethylene Oxychlorination
The current two-step process for the industrial process of vinyl chloride production involves CuCl2 catalyzed ethylene oxychlorination to ethylene dichloride followed by thermal cracking of the latter to vinyl chloride. To date, no industrial application of a one-step process is available. To close this gap, this work evaluates a wide range of self-prepared supported CeO2 and EuOCl catalysts for one-step production of vinyl chloride from ethylene in a fixed-bed reactor at 623 773 K and 1 bar using feed ratios of C2H4:HCl:O2:Ar:He = 3:3 6:1.5 6:3:82 89.5. Among all studied systems, CeO2/ZrO2 and CeO2/Zeolite MS show the highest activity but suffer from severe combustion of ethylene, forming COx, while 20 wt.% EuOCl/γ-Al2O3 leads to the best vinyl chloride selectivity of 87% at 15.6% C2H4 conversion with complete suppression of CO2 formation and only 4% selectivity to CO conversion for over 100 h on stream. Characterization by XRD and EDX mapping reveals that much of the Eu is present in non-active phases such as Al2Eu or EuAl4, indicating that alternative synthesis methods could be employed to better utilize the metal. A linear relationship between conversion and metal loading is found for this catalyst, indicating that always part of the used Eu is available as EuOCl, while the rest forms inactive europium aluminate species. Zeolite-supported EuOCl slightly outperforms EuOCl/γ Al2O3 in terms of total yield, but is prone to significant coking and is unstable. Even though a lot of Eu seems locked in inactive species on EuOCl/γ Al2O3, these results indicate possible savings of nearly 16,000 USD per kg of catalyst compared to a bulk EuOCl catalyst. These very promising findings constitute a crucial step for process intensification of polyvinyl chloride production and exploring the potential of supported EuOCl catalysts in industrially-relevant reactions.

Project 2 Abstract: Alkyne Semihydrogenation
Despite strongly suffering from poor noble metal utilization and a highly toxic selectivity modifier (Pb), the archetypal catalyst applied for the three-phase alkyne semihydrogenation, the Pb-doped Pd/CaCO3 (Lindlar catalyst), is still being utilized at industrial level. Inspired by the very recent strategies involving the modification of Pd with p-block elements (i.e., S), this work extrapolates the concept by preparing crystalline metal phosphides with controlled stoichiometry. To develop an affordable and environmentally-friendly alternative to traditional hydrogenation catalysts, nickel, a metal belonging to the same group as Pd and capable of splitting molecular hydrogen has been selected. Herein, a simple two-step synthesis procedure involving nontoxic precursors was used to synthesize bulk nickel phosphides with different stoichiometries (Ni2P, Ni5P4, and Ni12P5) by controlling the P:Ni ratios. To uncover structural and surface features, this catalyst family is characterized with an array of methods including X-ray diffraction (XRD), 31P magic-angle nuclear magnetic resonance (MAS-NMR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Bulk-sensitive techniques prove the successful preparation of pure phases while XPS analysis unravels the facile passivation occurring at the NixPy surface that persists even after reductive treatment. To assess the characteristic surface fingerprints of these materials, Ar sputtering was carried out at different penetration depths, reveling the presence of Ni+ and P-species. Continuous-flow three-phase hydrogenations of short-chain acetylenic compounds display that the oxidized layer covering the surface is reduced under reaction conditions, as evidenced by the induction period before reaching the steady state performance. To assess the impact of the phosphidation treatment on catalytic performance, the catalysts were benchmarked against a commercial Ni/SiO2-Al2O3 sample. While Ni/SiO2-Al2O3 presents very low selectivity to the alkene (the selectivity is about 10% at full conversion) attributed to the well-known tendency of naked nickel nanoparticles to form hydrides, the performance of nickel phosphides is highly selective and independent of P:Ni ratio. In line with previous findings on PdxS, kinetic tests indicate the occurrence of a dual-site mechanism where the alkyne and hydrogen do not compete for the same site.

This work is the subject of a publication of which I am a co-author, as cited below.

D. Albani; K. Karajovic; B. Tata; Q. Li; S. Mitchell; N. López; J. Pérez-Ramírez. Ensemble Design in Nickel Phosphide Catalysts for Alkyne Semi-Hydrogenation. ChemCatChem 2019. doi.org/10.1002/cctc.201801430

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2019-05

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The Effects of Nitrogen Fertilization of Wheatgrass on the South American Locust (Schistocerca cancellata)

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Locusts are a major crop pest in many parts of the world and different species are endemic to different countries. In Latin America, the South American Locust (Schistocerca cancellata) is the predominant species found mostly in Argentina, Chile, Bolivia, Paraguay,

Locusts are a major crop pest in many parts of the world and different species are endemic to different countries. In Latin America, the South American Locust (Schistocerca cancellata) is the predominant species found mostly in Argentina, Chile, Bolivia, Paraguay, and southern Brazil with Argentina being the most affected. Several control and management practices, including biological control, have been implemented in these countries in the past to control the locusts and reduce their impact on crop and vegetation, however, effective long-term control and management practices will require a detail understanding of how the predominant locust species in this region responds to resource variation. Research has shown that there is strong evidence that locusts, and many other organisms, will actively balance dietary macronutrients (protein, carbohydrates, and lipids) to optimize growth, survival, and/or reproduction. A study by Cease et. al, 2017, on the dietary preferences of the Mongolian locust (Oedaleus asiaticus) showed that it prefers diets that are high in carbohydrates over diets that are high in protein, in this case locusts self-selected a 1:2 ratio of protein:carbohydrate. This and many other studies provide vital insight into the nutritional and feeding preferences of these locust species but the effects that this difference in protein: carbohydrate preferences has on growth, egg production, flight potential, and survival has yet to be fully explored, hence, this study investigates the effects that nitrogen fertilization of wheatgrass will have on the growth, egg production, survival, and flight muscle mass of the South American locust in a controlled, laboratory environment.

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2018-05

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Aquatic Primary Productivity and Ecosystem Metabolism: Tres Rios Constructed Treatment Wetlands

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Freshwater ecosystems are increasingly threatened by anthropogenic eutrophication (Kolzau et al., 2014) and require mitigation efforts to prevent oxygen depletion and subsequent biodiversity loss. Tres Rios Constructed Treatment Wetland (CTW) relies on wetland ecosystem functioning to reduce nutrient concentrations in

Freshwater ecosystems are increasingly threatened by anthropogenic eutrophication (Kolzau et al., 2014) and require mitigation efforts to prevent oxygen depletion and subsequent biodiversity loss. Tres Rios Constructed Treatment Wetland (CTW) relies on wetland ecosystem functioning to reduce nutrient concentrations in order to meet regulatory guidelines. I investigated the impact of solar irradiance, temperature, and nutrient availability on aquatic net primary productivity, ecosystem respiration, and nutrient cycling using statistical analysis and quantitative modeling informed by field data generated by ASU’s Wetland Ecosystem Ecology Lab (WEEL) in partnership with the City of Phoenix Water Services Department. I found that the extent of daily solar insolation controls Aquatic Net Primary Productivity (ANPP) rates and the seasonal aquatic nutrient processing capacity of Tres Rios, resulting in the following approximate relationship: ANPP = 0.001344(W/m²) - 0.32634 (r² = 0.259; p = 0.005).

This formula was used to estimate the nutrient uptake performance of aquatic primary producers from sampling observations; ANPP accounted for 16.26 metric tons of system wide N uptake, while aquatic ER contributed 6.07 metric tons N of nighttime remineralization and 5.7 metric tons of N throughout the water column during the day. The estimated yearly net aquatic N flux is 4.49 metric tons uptake, compared to about 12 metric tons yearly N uptake by the vegetated marsh (Treese, 2019). However, not accounting for animal respiration results in an underestimation of system-wide N remineralization, and not accounting for soil processes results in an underestimation of N uptake.

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2020-05

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Analysis of Nitrogen Uptake in a Duckponics System

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Duckponics is an unconventional form of aquaponics that has recently been implemented by a small community in Washington State as an experiment in sustainable methods of food production. The community created the Duckponics system to test the possibility of using

Duckponics is an unconventional form of aquaponics that has recently been implemented by a small community in Washington State as an experiment in sustainable methods of food production. The community created the Duckponics system to test the possibility of using the waste of ducks present on the farm to fertilize crop plants. This research paper examines aspects of the nitrogen cycle within this system to determine the efficacy of nitrogen removal by plants and microbes. More specifically, the research examines (1) the microbial activity occurring in selected beds of the system, (2) the ability of hydroponic grow beds to retain inorganic nitrogen, and (3) how periodic flushing of the system affects nitrogen retention. Water data was collected in all system tanks using aquarium test strips, but water samples were collected for flow injection analysis in (1) one of the grow beds, (2) the duck pond, and (3) a control bed with no plants but filled with gravel and inoculated with the same bacteria from the grow bed. Samples were then analyzed for ammonia (NH4+-N) and combined nitrite and nitrate (NOx-N) concentrations. The results show that the treatment type (control, duck pond, or grow bed) was a significant (p<0.05) predictor of NH4+-N, NOx-N, and total inorganic nitrogen (TIN) in the porewater of the treatment beds. The grow bed was found to have 100% removal of TIN, whereas the control had 0% TIN removal (195% increase). Timing of the sample in relation to the flushing events was a moderately significant predictor of TIN, NH4+-N and NOx-N in the duck pond (p = 0.07 for TIN, p = 0.12 for NH4+-N, p = 0.11 for NOx-N), with an overall decrease in TIN after flood pulses. NH4+-N concentrations at the inlet and outlet were found to be significantly different in the grow bed (p=0.037), but not the control, and moderately significantly different (p<0.15) for NOx-N and TIN in the grow bed (p=0.072 for NOx-N, p=0.075 for TIN), but significant for the control (p=0.043). These findings show evidence of nitrification in the grow bed and control, plant presence significantly contributing to nitrogen removal in the grow bed, and some hydrologic flushing of NOx-N out of the duck pond during pump cycles.

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2016-05

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Community composition and nitrogen retention in an aridland wastewater treatment wetland

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City managers and policy makers are increasing looking to environmental systems to provide beneficial services for urban systems. Constructed wetland systems (CWS), highly managed and designed wetland ecosystems, are being utilized to remove pollution, particularly excess nitrogen (N), from treated

City managers and policy makers are increasing looking to environmental systems to provide beneficial services for urban systems. Constructed wetland systems (CWS), highly managed and designed wetland ecosystems, are being utilized to remove pollution, particularly excess nitrogen (N), from treated wastewater. Various wetland process remove N from effluent, such as denitrification, direct plant uptake, and soil accumulation. Emergent macrophytes provide direct uptake of N and improve conditions for microbially-mediated N processing. The role of different macrophytes species, however, is less understood and has primarily been examined in mesocosm and microcosm experiments and in mesic environments. I examined the effects of community composition on N removal and processing at the whole ecosystem scale in an aridland, constructed wetland (42 ha) through: 1) quantifying above- and belowground biomass and community composition from July 2011 \u2014 November 2012 using a non-destructive allometric technique, and; 2) quantifying macrophyte N content and direct macrophyte N uptake over the 2012 growing season. Average peak biomass in July 2011 & 2012 was 2,930 g dw/m2 and 2,340 g dw/m2, respectively. Typha spp. (Typha domingensis and Typha latifolia) comprised the majority (approximately 2/3) of live aboveground biomass throughout the sampling period. No statistically significant differences were observed in macrophyte N content among the six species present, with an overall average of 1.68% N in aboveground tissues and 1.29% N in belowground tissues. Per unit area of wetland, Typha spp. retained the most N (22 g/m2); total N retained by all species was 34 g/m2. System-wide direct plant N uptake was markedly lower than N input to the system and thus represented a small portion of system N processing. Soil accumulation of N also played a minor role, leaving denitrification as the likely process responsible for the majority of system N processing. Based on a literature review, macrophyte species composition likely influences denitrification through oxygen diffusion into soils and through the quality and quantity of carbon in leaf litter. While this study and the literature indicates Typha spp. may be the best species to promote wetland N processing, other considerations (e.g., bird habitat) and conditions (e.g., type of wastewater being treated) likely make mixed stands of macrophytes preferable in many applications. Additionally, this study demonstrated the importance of urban wetlands as scientific laboratories for scientists of all ages and as excellent stepping-off points for experiments of science-policy discourse.

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2013-05

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Documenting enhanced nitrogen removal in an aridland Constructed Treatment Wetland

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The rise in urban populations is encouraging cities to pursue sustainable water treatment services implementing constructed treatment wetlands (CTW). This is especially important in arid climates where water resources are scarce; however, research regarding aridland CTWs is limited. The Tres

The rise in urban populations is encouraging cities to pursue sustainable water treatment services implementing constructed treatment wetlands (CTW). This is especially important in arid climates where water resources are scarce; however, research regarding aridland CTWs is limited. The Tres Rios CTW in Phoenix, Arizona, USA, presents the tradeoff between greater water loss and enhanced nitrogen (N) removal. Previous research has suggested that water loss due to transpiration is replaced by a phenomenon termed the Biological Tide. This trend has been documented since 2011 by combining transpiration values with a nitrogen budget. Calculations were made at both the marsh and whole-system scale. The purpose of this paper is to demonstrate how the Biological Tide enhances N uptake throughout the CTW. Results indicate that about half of the nitrogen taken up by the vegetated marsh is associated with new water entering the marsh via the Biological Tide with even higher values during warmer months. Furthermore, it is this phenomenon that enhances N uptake throughout the year, on average, by 25.9% for nitrite, 9.54% for nitrate, and 4.84% for ammonium at the whole-system scale and 95.5%, 147%, and 118% within the marsh. This paper demonstrates the Biological Tide’s significant impact on enhanced N removal in an aridland CTW.

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2019-05