Matching Items (98)
Description
Mediation analysis is integral to psychology, investigating human behavior’s causal mechanisms. The diversity of explanations for human behavior has implications for the estimation and interpretation of statistical mediation models. Individuals can have similar observed outcomes while undergoing different causal processes or different observed outcomes while receiving the same treatment. Researchers can employ diverse strategies when studying individual differences in multiple mediation pathways, including individual fit measures and analysis of residuals. This dissertation investigates the use of individual residuals and fit measures to identify individual differences in multiple mediation pathways. More specifically, this study focuses on mediation model residuals in a heterogeneous population in which some people experience indirect effects through one mediator and others experience indirect effects through a different mediator. A simulation study investigates 162 conditions defined by effect size and sample size for three proposed methods: residual differences, delta z, and generalized Cook’s distance. Results indicate that analogs of Type 1 error rates are generally acceptable for the method of residual differences, but statistical power is limited. Likewise, neither delta z nor gCd could reliably distinguish between contrasts that had true effects and those that did not. The outcomes of this study reveal the potential for statistical measures of individual mediation. However, limitations related to unequal subpopulation variances, multiple dependent variables, the inherent relationship between direct effects and unestimated indirect effects, and minimal contrast effects require more research to develop a simple method that researchers can use on single data sets.
ContributorsSmyth, Heather Lynn (Author) / MacKinnon, David (Thesis advisor) / Tein, Jenn-Yun (Committee member) / McNeish, Daniel (Committee member) / Grimm, Kevin (Committee member) / Arizona State University (Publisher)
Created2022
Description
Lithium (Li) is a trace element in kerogen, but the content and isotopic distribution (δ7Li) in kerogen has not previously been quantified. Furthermore, kerogen has been overlooked as a potential source of Li to sedimentary porefluids and buried sediments. Thus, knowing the content and isotopic composition of Li derived from kerogen may have implications for research focused on the Li-isotopes of buried sediments (e.g., evaluating paleoclimate variations using marine carbonates).The objective of this work is to better understand the role of kerogen in the Li geochemical cycle. The research approach consisted of 1) developing reference materials and methodologies to measure the Li-contents and δ7Li of kerogen in-situ by Secondary Ion Mass Spectrometry, 2) surveying the Li-contents and δ7Li of kerogen bearing rocks from different depositional and diagenetic environments and 3) quantifying the Li-content and δ7Li variations in kerogen empirically in a field study and 4) experimentally through hydrous pyrolysis.
A survey of δ7Li of coals from depositional basins across the USA showed that thermally immature coals have light δ7Li values (–20 to – 10‰) compared to typical terrestrial materials (> –10‰) and the δ7Li of coal increases with burial temperature suggesting that 6Li is preferentially released from kerogen to porefluids during hydrocarbon generation. A field study was conducted on two Cretaceous coal seams in Colorado (USA) intruded by dikes (mafic and felsic) creating a temperature gradient from the intrusives into the country rock. Results showed that δ7Li values of the unmetamorphosed vitrinite macerals were up to 37‰ lighter than vitrinite macerals and coke within the contact metamorphosed coal.
To understand the significance of Li derived from kerogen during burial diagenesis, hydrous pyrolysis experiments of three coals were conducted. Results showed that Li is released from kerogen during hydrocarbon generation and could increase sedimentary porefluid Li-contents up to ~100 mg/L. The δ7Li of coals becomes heavier with increased temperature except where authigenic silicates may compete for the released Li. These results indicate that kerogen is a significant source of isotopically light Li to diagenetic fluids and is an important contributor to the global geochemical cycle.
ContributorsTeichert, Zebadiah (Author) / Williams, Lynda B. (Thesis advisor) / Bose, Maitrayee (Thesis advisor) / Hervig, Richard (Committee member) / Semken, Steven (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2022
Description
The Greater Obsidian Pool Area just south of the Mud Volcano area in Yellowstone National Park is an active and ever-changing hot spring region. Situated next to a lake in a meadow between several hills of glacial deposits, north of the Elephant Back rhyolite flow, a diverse group of hot springs has been developing. This study examines the geologic and geomorphic context of the hot springs, finding evidence for a previously undiscovered hydrothermal explosion crater and examining the deposits around the region that contribute to properties of the groundwater table. Hot spring geochemical measurements (Cl- and SO4-2) taken over the course of 20 years are used to determine fluid sourcing of the springs. The distribution of Cl-, an indicator of water-rock interaction, in the hot springs leads to the theory of a fissure delivering hydrothermal fluid in a line across the hot spring zone, with meteoric water from incoming groundwater diluting hot springs moving further from the fissure. A possible second dry fissure delivering mostly gas is also a possible explanation for some elevated sulfate concentrations in certain springs. The combination of geology, geomorphology, and geochemistry reveals how the surface and subsurface operate to generate different hot spring compositions.
ContributorsAlexander, Erin (Author) / Shock, Everett (Thesis director) / Whipple, Kelin (Committee member) / Barrett, The Honors College (Contributor) / School of Earth and Space Exploration (Contributor) / School of Molecular Sciences (Contributor)
Created2022-05
Description
Food insecurity is an economic and social condition involving limited or uncertain access to food. The problem of food insecurity in communities is influenced by economic conditions, food deserts, and barriers to accessing healthy food. Individuals experiencing food insecurity often endure concurrent problems of financial instability, hunger, and poor mental and physical health. Public and non-profit services in the U.S., such as the federally supported Supplemental Nutrition Assistance Program (SNAP) and community food banks, provide food-related assistance to individuals who are at a high risk of experiencing food insecurity. Unfortunately, many individuals who qualify for these services still experience food insecurity due to barriers preventing them from accessing food, which may include inadequate finances, transportation, skills, and information. Effective approaches for removing barriers that prevent individuals from accessing food are needed to mitigate the increased risk of hunger, nutritional deficiencies, and chronic disease among vulnerable populations. This dissertation tested a novel food insecurity intervention using informational nudges to promote food security through the elimination of information barriers to accessing food. The intervention used in this mixed-methods feasibility study consisted of informational nudges in the form of weekly text messages that were sent to food pantry clients experiencing food insecurity. The study aims were to test the efficacy and acceptability of the intervention by examining whether the informational nudges could enhance food pantry utilization, increase SNAP registration, and promote food security. Quantitative study results showed a lower prevalence of food insecurity in the intervention group than the control group. Qualitative findings revealed how the intervention group found the text messages to be helpful and informative. These study findings can enhance future food insecurity interventions aiming to eliminate barriers that prevent individuals who are food insecure from accessing healthy food.
ContributorsRoyer, Michael F. (Author) / Wharton, Christopher (Thesis advisor) / Buman, Matthew (Committee member) / Der Ananian, Cheryl (Committee member) / MacKinnon, David (Committee member) / Ohri-Vachaspati, Punam (Committee member) / Arizona State University (Publisher)
Created2023
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
Atmospheric particulate matter (PM) has a pronounced effect on our climate, and exposure to PM causes negative health outcomes and elevated mortality rates in urban populations. Reactions that occur in fog can form new secondary organic aerosol material from gas-phase species or primary organic aerosols. It is important to understand these reactions, as well as how organic material is scavenged and deposited, so that climate and health effects can be fully assessed. Stable carbon isotopes have been used widely in studying gas- and particle-phase atmospheric chemistry. However, the processing of organic matter by fog has not yet been studied, even though stable isotopes can be used to track all aspects of atmospheric processing, from particle formation, particle scavenging, reactions that form secondary organic aerosol material, and particle deposition. Here, carbon isotope analysis is used for the first time to assess the processing of carbonaceous particles by fog.
This work first compares carbon isotope measurements (δ13C) of particulate matter and fog from locations across the globe to assess how different primary aerosol sources are reflected in the atmosphere. Three field campaigns are then discussed that highlight different aspects of PM formation, composition, and processing. In Tempe, AZ, seasonal and size-dependent differences in the δ13C of total carbon and n-alkanes in PM were studied. δ13C was influenced by seasonal trends, including inversion, transport, population density, and photochemical activity. Variations in δ13C among particle size fractions were caused by sources that generate particles in different size modes.
An analysis of PM from urban and suburban sites in northeastern France shows how both fog and rain can cause measurable changes in the δ13C of PM. The δ13C of PM was consistent over time when no weather events occurred, but particles were isotopically depleted by up to 1.1‰ in the presence of fog due to preferential scavenging of larger isotopically enriched particles. Finally, the δ13C of the dissolved organic carbon in fog collected on the coast of Southern California is discussed. Here, temporal depletion of the δ13C of fog by up to 1.2‰ demonstrates its use in observing the scavenging and deposition of organic PM.
This work first compares carbon isotope measurements (δ13C) of particulate matter and fog from locations across the globe to assess how different primary aerosol sources are reflected in the atmosphere. Three field campaigns are then discussed that highlight different aspects of PM formation, composition, and processing. In Tempe, AZ, seasonal and size-dependent differences in the δ13C of total carbon and n-alkanes in PM were studied. δ13C was influenced by seasonal trends, including inversion, transport, population density, and photochemical activity. Variations in δ13C among particle size fractions were caused by sources that generate particles in different size modes.
An analysis of PM from urban and suburban sites in northeastern France shows how both fog and rain can cause measurable changes in the δ13C of PM. The δ13C of PM was consistent over time when no weather events occurred, but particles were isotopically depleted by up to 1.1‰ in the presence of fog due to preferential scavenging of larger isotopically enriched particles. Finally, the δ13C of the dissolved organic carbon in fog collected on the coast of Southern California is discussed. Here, temporal depletion of the δ13C of fog by up to 1.2‰ demonstrates its use in observing the scavenging and deposition of organic PM.
ContributorsNapolitano, Denise (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2018
Description
Longitudinal recursive partitioning (LRP) is a tree-based method for longitudinal data. It takes a sample of individuals that were each measured repeatedly across time, and it splits them based on a set of covariates such that individuals with similar trajectories become grouped together into nodes. LRP does this by fitting a mixed-effects model to each node every time that it becomes partitioned and extracting the deviance, which is the measure of node purity. LRP is implemented using the classification and regression tree algorithm, which suffers from a variable selection bias and does not guarantee reaching a global optimum. Additionally, fitting mixed-effects models to each potential split only to extract the deviance and discard the rest of the information is a computationally intensive procedure. Therefore, in this dissertation, I address the high computational demand, variable selection bias, and local optimum solution. I propose three approximation methods that reduce the computational demand of LRP, and at the same time, allow for a straightforward extension to recursive partitioning algorithms that do not have a variable selection bias and can reach the global optimum solution. In the three proposed approximations, a mixed-effects model is fit to the full data, and the growth curve coefficients for each individual are extracted. Then, (1) a principal component analysis is fit to the set of coefficients and the principal component score is extracted for each individual, (2) a one-factor model is fit to the coefficients and the factor score is extracted, or (3) the coefficients are summed. The three methods result in each individual having a single score that represents the growth curve trajectory. Therefore, now that the outcome is a single score for each individual, any tree-based method may be used for partitioning the data and group the individuals together. Once the individuals are assigned to their final nodes, a mixed-effects model is fit to each terminal node with the individuals belonging to it.
I conduct a simulation study, where I show that the approximation methods achieve the goals proposed while maintaining a similar level of out-of-sample prediction accuracy as LRP. I then illustrate and compare the methods using an applied data.
I conduct a simulation study, where I show that the approximation methods achieve the goals proposed while maintaining a similar level of out-of-sample prediction accuracy as LRP. I then illustrate and compare the methods using an applied data.
ContributorsStegmann, Gabriela (Author) / Grimm, Kevin (Thesis advisor) / Edwards, Michael (Committee member) / MacKinnon, David (Committee member) / McNeish, Daniel (Committee member) / Arizona State University (Publisher)
Created2019
Description
There is a need to reinvent evidence-based interventions (EBIs) for pediatric anxiety problems to better address the demands of real-word service delivery settings and achieve public health impact. The time- and resource-intensive nature of most EBIs for youth anxiety has frequently been noted as a barrier to the utilization of EBIs in community settings, leading to increased attention towards exploring the viability of briefer, more accessible protocols. Principally, this research reports between-group effect sizes from brief-interventions targeting pediatric anxiety and classifies each as well-established, probably efficacious, possibly efficacious, experimental, or questionable. brief interventions yielded an overall mean effect size of 0.19 on pediatric anxiety outcomes from pre to post. Effect sizes varied significantly by level of intervention: Pre to post-intervention effects were strongest for brief-treatments (0.35), followed by brief-targeted prevention (0.22), and weakest for brief-universal prevention (0.09). No participant or other intervention characteristic emerged as significant moderators of effect sizes. In terms of standard of evidence, one brief intervention is well-established, and five are probably efficacious, with most drawing on cognitive and behavioral change procedures and/or family systems models. At this juncture, the minimal intervention needed for clinical change in pediatric anxiety points to in-vivo exposures for specific phobias (~3 hours), cognitive-behavioral therapy (CBT) with social skills training (~3 hours), and CBT based parent training (~6 hours, eight digital modules with clinician support). This research concludes with a discussion on limitations to available brief EBIs, practice guidelines, and future research needed to capitalize on the viability of briefer protocols in enhancing access to, and impact of, evidence-based care in the real-world.
ContributorsStoll, Ryan (Author) / Pina, Armando A. (Thesis advisor) / Gonzales, Nancy (Committee member) / MacKinnon, David (Committee member) / Perez, Marisol (Committee member) / Arizona State University (Publisher)
Created2019
Description
Chemical and physical interactions of flowing ice and rock have inexorably shaped planetary surfaces. Weathering in glacial environments is a significant link in biogeochemical cycles – carbon and strontium – on Earth, and may have once played an important role in altering Mars’ surface. Despite growing recognition of the importance of low-temperature chemical weathering, these processes are still not well understood. Debris-coated glaciers are also present on Mars, emphasizing the need to study ice-related processes in the evolution of planetary surfaces. During Earth’s history, subglacial environments are thought to have sheltered communities of microorganisms from extreme climate variations. On Amazonian Mars, glaciers such as lobate debris aprons (LDA) could have hosted chemolithotrophic communities, making Mars’ present glaciers candidates for life preservation. This study characterizes glacial processes on both Earth and Mars.
Chemical weathering at Robertson Glacier, a small alpine glacier in the Canadian Rocky Mountains, is examined with a multidisciplinary approach. The relative proportions of differing dissolution reactions at various stages in the glacial system are empirically determined using aqueous geochemistry. Synthesis of laboratory and orbital thermal infrared spectroscopy allows identification of dissolution rinds on hand samples and characterization of carbonate dissolution signals at orbital scales, while chemical and morphological evidence for thin, discontinuous weathering rinds at microscales are evident from electron microscopy. Subglacial dissolution rates are found to outpace those of the proglacial till plain; biologically-mediated pyrite oxidation drives the bulk of this acidic weathering.
Second, the area-elevation relationship, or hypsometry, of LDA in the midlatitudes of Mars is characterized. These glaciers are believed to have formed ~500 Ma during a climate excursion. Hypsometric measurements of these debris-covered glaciers enable insight into past flow regimes and drive predictions about past climate scenarios. The LDA in this study fall into three major groups, strongly dependent on basal elevation, implying regional and climatic controls on ice formation and flow.
I show that biologically-mediated mineral reactions drive high subglacial dissolution rates, such that variations within the valley can be detected with remote sensing techniques. In future work, these insights can be applied to examining Mars’ glacial regions for signs of chemical alteration and biosignatures.
Chemical weathering at Robertson Glacier, a small alpine glacier in the Canadian Rocky Mountains, is examined with a multidisciplinary approach. The relative proportions of differing dissolution reactions at various stages in the glacial system are empirically determined using aqueous geochemistry. Synthesis of laboratory and orbital thermal infrared spectroscopy allows identification of dissolution rinds on hand samples and characterization of carbonate dissolution signals at orbital scales, while chemical and morphological evidence for thin, discontinuous weathering rinds at microscales are evident from electron microscopy. Subglacial dissolution rates are found to outpace those of the proglacial till plain; biologically-mediated pyrite oxidation drives the bulk of this acidic weathering.
Second, the area-elevation relationship, or hypsometry, of LDA in the midlatitudes of Mars is characterized. These glaciers are believed to have formed ~500 Ma during a climate excursion. Hypsometric measurements of these debris-covered glaciers enable insight into past flow regimes and drive predictions about past climate scenarios. The LDA in this study fall into three major groups, strongly dependent on basal elevation, implying regional and climatic controls on ice formation and flow.
I show that biologically-mediated mineral reactions drive high subglacial dissolution rates, such that variations within the valley can be detected with remote sensing techniques. In future work, these insights can be applied to examining Mars’ glacial regions for signs of chemical alteration and biosignatures.
ContributorsRutledge, Alicia Marie (Author) / Christensen, Philip R. (Thesis advisor) / Shock, Everett (Committee member) / Clarke, Amanda (Committee member) / Sharp, Thomas (Committee member) / Whipple, Kelin (Committee member) / Arizona State University (Publisher)
Created2015
Description
Natural variations in 238U/235U of marine carbonates might provide a useful way of constraining redox conditions of ancient environments. In order to evaluate the reliability of this proxy, we conducted aragonite and calcite coprecipitation experiments at pH ~7.5 and ~ 8.5 to study possible U isotope fractionation during incorporation into these minerals.
Small but significant U isotope fractionation was observed in aragonite experiments at pH ~ 8.5, with heavier U in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007+0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3 (aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism.
These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2, [Ca], or [Mg] concentrations. In general, these effects are likely to be small (<0.13 ‰), but are nevertheless potentially significant because of the small natural range of variation of 238U/235U.
Small but significant U isotope fractionation was observed in aragonite experiments at pH ~ 8.5, with heavier U in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007+0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3 (aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism.
These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2, [Ca], or [Mg] concentrations. In general, these effects are likely to be small (<0.13 ‰), but are nevertheless potentially significant because of the small natural range of variation of 238U/235U.
ContributorsChen, Xinming (Author) / Anbar, Ariel (Thesis advisor) / Herckes, Pierre (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2015