Filtering by
- All Subjects: Water
- Creators: Chemical Engineering Program
- Status: Published
In two-week natural sunlight photo-oxidation experiments the DOC concentration did not change, while the SUVA254 and TF decreased. In addition, the FI and ‘freshness’ increased and HIX decreased during photo-oxidation. Photo-oxidation can explain the upstream to downstream trends for TF, FI, HIX, and freshness observed in river water. Serial photo-oxidation and biodegradation experiments were performed on water collected from three sites along the Colorado River. Bulk DOC concentration in all samples decreased during the biodegradation portion of the study, but DOC bioavailability was lower in samples that were photo-oxidized prior to the bioavailability study.
The upstream to downstream trends in DOC concentration and composition along the river can be explained by a combination of photo-chemical and microbial degradation. The bulk DOC concentration change is primarily driven by microbial degradation, while the changes in the composition of the fluorescent DOC are driven by photo-oxidation.
Permanently shadowed regions (PSRs) at the lunar poles may contain substantial water ice, but radar signatures at PSRs could indicate water ice or large block populations. Mini-RF radar and Lunar Reconnaissance Orbiter Camera Narrow Angle Camera (LROC NAC) products were used to assess block abundances where radar signatures indicated potential ice deposits. While the majority of PSRs in this study indicated large block populations and a low likelihood of water ice, one crater – Rozhdestvenskiy N – showed indirect indications of water ice in its interior.
Chloride deposits indicate regions where the last substantial liquid water existed on Mars. Major ion abundances and expected precipitation sequences of terrestrial chloride brines could provide context for assessing the provenance of martian chloride deposits. Chloride minerals are most readily distinguished in the far-infrared (45+ μm), where their fundamental absorption features are strongest. Multiple chloride compositions and textures were characterized in far-infrared emission for the first time. Systematic variations in the spectra were observed; these variations will allow chloride mineralogy to be determined and large variations in texture to be constrained.
In the present day, recurring slope lineae (RSL) may indicate water flow, but fresh water is not stable on Mars. However, dissolved chloride could allow liquid water to flow transiently. Using Thermal Emission Imaging System (THEMIS) data, I determined that RSL are most likely not fed by chloride-rich brines on Mars. Substantial amounts of salt would be consumed to produce a surface water flow; therefore, these features are therefore thought to instead be surface darkening due to capillary wicking.
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
More than half of all accessible freshwater has been appropriated for human use, and a substantial portion of terrestrial ecosystems have been transformed by human action. These impacts are heaviest in urban ecosystems, where impervious surfaces increase runoff, water delivery and stormflows are managed heavily, and there are substantial anthropogenic sources of nitrogen (N). Urbanization also frequently results in creation of intentional novel ecosystems. These "designed" ecosystems are fashioned to fulfill particular needs of the residents, or ecosystem services. In the Phoenix, Arizona area, the augmentation and redistribution of water has resulted in numerous component ecosystems that are atypical for a desert environment. Because these systems combine N loading with the presence of water, they may be hot spots of biogeochemical activity. The research presented here illustrates the types of hydrological modifications typical of desert cities and documents the extent and distribution of common designed aquatic ecosystems in the Phoenix metropolitan area: artificial lakes and stormwater retention basins. While both ecosystems were designed for other purposes (recreation/aesthetics and flood abatement, respectively), they have the potential to provide the added ecosystem service of N removal via denitrification. However, denitrification in urban lakes is likely to be limited by the rate of diffusion of nitrate into the sediment. Retention basins export some nitrate to groundwater, but grassy basins have higher denitrification rates than xeriscaped ones, due to higher soil moisture and organic matter content. An economic valuation of environmental amenities demonstrates the importance of abundant vegetation, proximity to water, and lower summer temperatures throughout the region. These amenities all may be provided by designed, water-intensive ecosystems. Some ecosystems are specifically designed for multiple uses, but maximizing one ecosystem service often entails trade-offs with other services. Further investigation into the distribution, bundling, and tradeoffs among water-related ecosystem services shows that some types of services are constrained by the hydrogeomorphology of the area, while for others human engineering and the creation of designed ecosystems has enabled the delivery of hydrologic ecosystem services independent of natural constraints.
The outlying cities of Phoenix's West Metropolitan experienced rapid growth in the past ten years. This trend is only going to continue with an average expected growth of 449-891% between 2000 and 2035 (ADOT, 2012). Phoenix is not new to growth and has consistently seen swaths of people added to its population. This raises the question of what happened to the people who lived in Phoenix's West Valley during this period of rapid change and growth in their communities? What are their stories and what do their stories reveal about the broader public history of change in Phoenix's West Valley? In consideration of these questions, the community oral histories of eight residents from the West Valley were collected to add historical nuance to the limited archival records available in the area. From this collection, the previous notion of "post-war boomtowns” describing Phoenix’s West Valley was revealed to be highly inaccurate and dismissive of the residents' experiences who lived and formed their lives there.