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Atmospheric particulate matter has a substantial impact on global climate due to its ability to absorb/scatter solar radiation and act as cloud condensation nuclei (CCN). Yet, little is known about marine aerosol, in particular, the carbonaceous fraction. In the present work, particulate matter was collected, using High Volume (HiVol) samplers, onto quartz fiber substrates during a series of research cruises on the Atlantic Ocean. Samples were collected on board the R/V Endeavor on West–East (March–April, 2006) and East–West (June–July, 2006) transects in the North Atlantic, as well as on the R/V Polarstern during a North–South (October–November, 2005) transect along the western coast of Europe and Africa. The aerosol total carbon (TC) concentrations for the West–East (Narragansett, RI, USA to Nice, France) and East–West (Heraklion, Crete, Greece to Narragansett, RI, USA) transects were generally low over the open ocean (0.36±0.14 μg C/m3) and increased as the ship approached coastal areas (2.18±1.37 μg C/m3), due to increased terrestrial/anthropogenic aerosol inputs. The TC for the North–South transect samples decreased in the southern hemisphere with the exception of samples collected near the 15th parallel where calculations indicate the air mass back trajectories originated from the continent. Seasonal variation in organic carbon (OC) was seen in the northern hemisphere open ocean samples with average values of 0.45 μg/m3 and 0.26 μg/m3 for spring and summer, respectively. These low summer time values are consistent with SeaWiFS satellite images that show decreasing chlorophyll a concentration (a proxy for phytoplankton biomass) in the summer. There is also a statistically significant (p<0.05) decline in surface water fluorescence in the summer. Moreover, examination of water–soluble organic carbon (WSOC) shows that the summer aerosol samples appear to have a higher fraction of the lower molecular weight material, indicating that the samples may be more oxidized (aged). The seasonal variation in aerosol content seen during the two 2006 cruises is evidence that a primary biological marine source is a significant contributor to the carbonaceous particulate in the marine atmosphere and is consistent with previous studies of clean marine air masses.
ContributorsHill, Hansina Rae (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Hartnett, Hilairy (Committee member) / Arizona State University (Publisher)
Created2011
Description
With a recent shift to a more environmentally conscious society, low-carbon and non-carbon producing energy production methods are being investigated and applied all over the world. Of these methods, fuel cells show great potential for clean energy production. A fuel cell is an electrochemical energy conversion device which directly converts chemical energy into electrical energy. Proton exchange membrane fuel cells (PEMFCs) are a highly researched energy source for automotive and stationary power applications. In order to produce the power required to meet Department of Energy requirements, platinum (Pt) must be used as a catalyst material in PEMFCs. Platinum, however, is very expensive and extensive research is being conducted to develop ways to reduce the amount of platinum used in PEMFCs. In the current study, three catalyst synthesis techniques were investigated and evaluated on their effectiveness to produce platinum-on copper (Pt@Cu) core-shell nanocatalyst on multi-walled carbon nanotube (MWCNT) support material. These three methods were direct deposition method, two-phase surfactant method, and single-phase surfactant method, in which direct deposition did not use a surfactant for particle size control and the surfactant methods did. The catalyst materials synthesized were evaluated by visual inspection and fuel cell performance. Samples which produced high fuel cell power output were evaluated using transmission electron microscopy (TEM) imaging. After evaluation, it was concluded that the direct deposition technique was effective in synthesizing Pt@Cu core-shell nanocatalyst on MWCNTs support when a rinsing process was used before adding platinum. The peak power density achieved by the rinsed core-shell catalyst was 618 mW.cm-2 , 13 percent greater than that of commercial platinum-carbon (Pt/C) catalyst. Transmission electron microscopy imaging revealed the core-shell catalyst contained Pt shells and platinum-copper alloy cores. Rinsing with deionized (DI) water was shown to be a crucial step in core-shell catalyst deposition as it reduced the number of platinum colloids on the carbon nanotube surface. After evaluation, it was concluded that the two-phase surfactant and single-phase surfactant synthesis methods were not effective at producing core-shell nanocatalyst with the parameters investigated.
ContributorsAdame, Anthony (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Peng, Xihong (Committee member) / Tamizhmani, Govindasamy (Committee member) / Arizona State University (Publisher)
Created2012
Description
Low temperature fuel cells are very attractive energy conversion technology for automotive applications due to their qualities of being clean, quiet, efficient and good peak power densities. However, due to high cost and limited durability and reliability, commercialization of this technology has not been possible as yet. The high fuel cell cost is mostly due to the expensive noble catalyst Pt. Alkaline fuel cell (AFC) systems, have potential to make use of non-noble catalysts and thus, provides with a solution of overall lower cost. Therefore, this issue has been addressed in this thesis work. Hydrogen-oxygen fuel cells using an alkaline anion exchange membrane were prepared and evaluated. Various non-platinum catalyst materials were investigated by fabricating membrane-electrode assemblies (MEAs) using Tokuyama membrane (# A201) and compared with commercial noble metal catalysts. Co and Fe phthalocyanine catalyst materials were synthesized using multi-walled carbon nanotubes (MWCNTs) as support materials. X-ray photoelectron spectroscopic study was conducted in order to examine the surface composition. The electroreduction of oxygen has been investigated on Fe phthalocyanine/MWCNT, Co phthalocyanine/MWCNT and commercial Pt/C catalysts. The oxygen reduction reaction kinetics on these catalyst materials were evaluated using rotating disk electrodes in 0.1 M KOH solution and the current density values were consistently higher for Co phthalocyanine based electrodes compared to Fe phthalocyanine. The fuel cell performance of the MEAs with Co and Fe phthalocyanines and Tanaka Kikinzoku Kogyo Pt/C cathode catalysts were 100, 60 and 120 mW cm-2 using H22 and O2 gases. This thesis also includes work on synthesizing nitrogen doped MWCNTs using post-doping and In-Situ methods. Post-doped N-MWNCTs were prepared through heat treatment with NH4OH as nitrogen source. Characterization was done through fuel cell testing, which gave peak power density ~40mW.cm-2. For In-Situ N-MWCT, pyridine was used as nitrogen source. The sample characterization was done using Raman spectroscopy and RBS, which showed the presence ~3 at.% of nitrogen on the carbon surface.
ContributorsShah, QuratulAin Jawed (Author) / Madakannan, Arunachalanadar (Thesis advisor) / Tamizhmani, Govindasamy (Committee member) / Macia, Narciso (Committee member) / Arizona State University (Publisher)
Created2012
Description
Accidental wetlands have been created on the bed of the Salt River and are fed by storm-water outfalls discharging at various sections of the Phoenix Metropolitan Area. Water discharges from these outfalls throughout the year, during both dry conditions (base flow) and during rain events (storm flow). In this study, DOC content and composition was studied during these two flow conditions, in the outfalls and along the wetland flow path. The importance of DOC lies in its role in transporting carbon via water movement, between different parts of a landscape, and therefore between pools in the ecosystem. Urbanization has influenced content and composition of DOC entering the accidental urban wetland via outfalls as they represent watersheds from different areas in Phoenix. First, DOC load exhibited higher quantities during stormflow compared to baseflow conditions. Second, DOC load and fluorescence analysis outcomes concluded the outfalls are different from each other. The inputs of water on the north side of the channel represent City of Phoenix watersheds were similar to each other and had high DOC load. The northern outfalls are both different in load and composition from the outfall pipe on the southern bank of the wetland as it represents South Mountain watershed. Fluorescence analysis results also concluded compositional changes occurred along the wetland flow path during both stormflow and baseflow conditions. In this study, it was explored how urbanization and the associated changes in hydrology and geomorphology have affected a desert wetland's carbon content.
ContributorsBone, Stephanie Rosalia (Author) / Hartnett, Hilairy (Thesis director) / Palta, Monica (Committee member) / Mascaro, Giuseppe (Committee member) / Civil, Environmental and Sustainable Engineering Programs (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Tempe Town Lake is the site of fifteen years’ worth of chemical data collection by ASU researchers. In 2018 the dataSONDE, an instrument capable of measuring different water quality parameters every thirty minutes for a month at a time was installed in the lake. The SONDE has the potential to completely reduce the need for sampling by hand. Before the SONDE becomes the sole means of gathering data, it is important to verify its accuracy. In this study, the measurements gathered by the SONDE (pH, dissolved oxygen, temperature, conductivity and colored dissolved organic matter) were compared to measurements gathered using the verified methods from the past fifteen years.
ContributorsSauer, Elinor Rayne (Author) / Hartnett, Hilairy (Thesis director) / Glaser, Donald (Committee member) / Shock, Everett (Committee member) / Historical, Philosophical & Religious Studies (Contributor) / School of Molecular Sciences (Contributor) / School of Life Sciences (Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2020-12
Description
N-nitrosodimethylamine (NDMA) is a probable human carcinogen that has been detected in various environments including the atmosphere, clouds, surface waters, and drinking water. NDMA can form through natural reactions in the aqueous phase of the atmosphere and it can form as a disinfection byproduct in water treatment. Due to its carcinogenic nature, it is important to understand the mechanism of formation of NDMA in both engineered processes such as water treatment and in natural processes in fogs and clouds. NDMA might form through the reaction of chloramines with amines in both cases. This work analyzes polydiallyldimethyl ammonium chloride (PolyDADMAC), which is the most commonly used polymer at drinking water treatment plants and has the potential to form NDMA if free polymer is present during the chloramination (disinfection) process. The composition of industrial polyDADMAC solutions is not well understood and is difficult to analyze. This work uses 1H and 13C nuclear magnetic resonance (NMR) to analyze the polymer solution composition. Both 1H and 13C NMR allow investigation of the presence of trace impurities in the solution, gather structural information such as chain length, and inform on reaction mechanisms. The primary impurities of concern for NDMA formation were identified as dimethylamine (DMA) and short-chain oligomers of the polyDADMAC. 13C NMR was further used to confirm that NDMA likely forms from polyDADMAC via a Hofmann elimination.
Chloramines might also form in fogs and clouds although to date the potential for chloramines to form NDMA in atmospheric fog and cloud droplets has not been investigated. This work uses computational modeling to determine that at reported atmospheric conditions, the chloramine pathway contributes to less than 0.01% NDMA formation. The numerical modeling identified a need for more atmospheric HOCl measurements. This work proposes a concept of using HOCl to react to form chloramine, which can react to form NDMA as a way to quantify atmospheric HOCl.
ContributorsDonovan, Samantha Jo (Author) / Herckes, Pierre (Thesis advisor) / Westerhoff, Paul (Committee member) / Hayes, Mark (Committee member) / Arizona State University (Publisher)
Created2022
Description
ABSTRACT
Tempe, Arizona can experience high atmospheric particulate matter episodes, both in winter and in summer. In summer, such events might be due to dust storms or wildfires, while in the wintertime, domestic wood burning (fireplaces and heating) tends to be a major contributor. In this study, it was investigated that the particulate matter concentrations and composition for select summertime and wintertime events in Tempe, expected to have high concentrations and possibly biomass burning impacts. Summertime concentrations on the selected days were low except for a dust storm event. In the winter events, across the New Year holiday, concentrations were substantial, especially on New Year's morning because of the fireworks, although precipitation impacted the concentrations. Chemical analysis of bulk organic (OC) and elemental (EC) carbon shows a high ratio of OC/EC, indicative of substantial secondary organic aerosol contributions or biomass burning. Investigation of biomass burning specific molecular markers, such as levoglucosan, using gas chromatography mass spectrometry, showed detectable concentrations during wintertime, confirming wood burning as a significant source of atmospheric particulate matter. In summer, levoglucosan was detected but during the times investigated, wood smoke was not a dominant source of particulate matter. Finally, particulate polycyclic aromatic hydrocarbons (PAH) of burning origin were also investigated because of their toxicity. PAH concentrations showed a clear dependence of temperature with lower molecular weighted (LMW) PAHs being less abundant in the summertime in the particulate matter because of their volatility. The use of diagnostic PAH ratios confirmed the importance of combustion sources for the PAH albeit different ones in summer compared to winter events.
ContributorsAbel, Parker Stephen (Author) / Herckes, Pierre (Thesis advisor) / Xu, Jie (Committee member) / Fraser, Matthew (Committee member) / Arizona State University (Publisher)
Created2024
Description
Pollen allergies are common in the United States, especially in Arizona. In addition to more people experiencing allergies, the allergies themselves are worse, with people reporting more severe and longer lasting symptoms, after moving to Arizona. Potential reasons behind this include a longer blooming season in the state, a lack of rain to wash out pollen from the atmosphere, and compounding factors of poor air quality. One significant contributor to poor air quality are high ozone levels in urban areas like Phoenix. The goal of this study is to determine if ozone and pollen interact in a way that changes pollen physically or chemically. Ragweed pollen was placed in a chamber and exposed to low, medium, and high levels of ozone for 6-72 hours corresponding to different exposure doses. Exposed and non-exposed pollen was analyzed for physical changes in the pollen grain using scanning electron microscopy (SEM). Chemical changes were investigated using Fourier Transform Infrared Spectroscopy (FT-IR). Finally, exposed and non-exposed pollen was analyzed for changes in lipid profiles using gas chromatography mass spectrometry (GC/MS). SEM analysis found that when ragweed pollen is exposed to high ozone levels (60-100 ppm, > 48 hours), pollen grains become damaged. The same exposure level results in chemical changes in the pollen that are detectable by FT-IR. A higher ozone dose results in worse physical damage and increased changes in the lipid profile. Future research should study a wider ranges of exposure doses and relate the physicochemical changes to differences in immune response.
ContributorsKing, Lily (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew (Committee member) / Levitus, Marcia (Committee member) / Arizona State University (Publisher)
Created2024
Description
Microplastics, plastics smaller than 5 mm, are an emerging concern worldwide due to their potential adverse effects on the environment and human health. Microplastics have the potential to biomagnify through the food chain, and are prone to adsorbing organic pollutants and heavy metals. Therefore, there is an urgent need to assess the extent of microplastic contamination in different environments. The occurrence of microplastics in the atmosphere of Tempe, AZ was investigated and results show concentrations as high as 1.1 microplastics/m3. The most abundant identified polymer was polyvinyl chloride. However, chemical characterization is fraught with challenges, with a majority of microplastics remaining chemically unidentified. Laboratory experiments simulating weathering of microplastics revealed that Raman spectra of microplastics change over time due to weathering processes. This work also studied the spatial variation of microplastics in soil in Phoenix and the surrounding areas of the Sonoran Desert, and microplastic abundances ranged from 122 to 1299 microplastics/kg with no clear trends between different locations, and substantial total deposition of microplastics occurring in the same location with resuspension and redistribution of deposited microplastics likely contributing to unclear spatial trends. Temporal variation of soil microplastics from 2005 to 2015 show a systematic increase in the abundance of microplastics. Polyethylene was prominent in all soil samples.
Further, recreational surface waters were investigated as a potential source of microplastics in aquatic environments. The temporal variation of microplastics in the Salt River, AZ over the course of one day depicted an increase of 8 times in microplastic concentration at peak activity time of 16:00 hr compared to 8:00 hr. Concurrently, microplastic concentrations in surface water samples from apartment community swimming pools in Tempe, AZ depicted substantial variability with concentrations as high as 254,574 MPs/m3. Polyester and Polyamide fibers were prevalent in surface water samples, indicating a release from synthetic fabrics. Finally, a method for distinguishing tire wear microplastics from soot in ambient aerosol samples was developed using Programmed Thermal Analysis, that allows for the quantification of Elemental Carbon. The method was successfully applied on urban aerosol samples with results depicting substantial fractions of tire wear in urban atmospheric environments.
ContributorsChandrakanthan, Kanchana (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2024
Description
The volume of end-of-life photovoltaic (PV) modules is increasing as the global PV market increases, and the global PV waste streams are expected to reach 250,000 metric tons by the end of 2020. If the recycling processes are not in place, there would be 60 million tons of end-of-life PV modules lying in the landfills by 2050, that may not become a not-so-sustainable way of sourcing energy since all PV modules could contain certain amount of toxic substances. Currently in the United States, PV modules are categorized as general waste and can be disposed in landfills. However, potential leaching of toxic chemicals and materials, if any, from broken end-of-life modules may pose health or environmental risks. There is no standard procedure to remove samples from PV modules for chemical toxicity testing in the Toxicity Characteristic Leaching Procedure (TCLP) laboratories as per EPA 1311 standard. The main objective of this thesis is to develop an unbiased sampling approach for the TCLP testing of PV modules. The TCLP testing was concentrated only for the laminate part of the modules, as they are already existing recycling technologies for the frame and junction box components of PV modules. Four different sample removal methods have been applied to the laminates of five different module manufacturers: coring approach, cell-cut approach, strip-cut approach, and hybrid approach. These removed samples were sent to two different TCLP laboratories, and TCLP results were tested for repeatability within a lab and reproducibility between the labs. The pros and cons of each sample removal method have been explored and the influence of sample removal methods on the variability of TCLP results has been discussed. To reduce the variability of TCLP results to an acceptable level, additional improvements in the coring approach, the best of the four tested options, are still needed.
ContributorsLeslie, Joswin (Author) / Tamizhmani, Govindasamy (Thesis advisor) / Srinivasan, Devarajan (Committee member) / Kuitche, Joseph (Committee member) / Arizona State University (Publisher)
Created2018