Graduate Theses & Dissertations

Characterization of Synthetic and Natural Se8 and Related SenSm Compounds by Gas Chromatography-Mass Spectrometry
Elemental selenium has been extensively quantitatively measured in sediments; however, its physical composition is largely unknown, despite it being the dominant selenium species in some reducing environments. Here, for the first time, it is shown that small, cyclic selenium compounds can account for a quantitatively-relevant fraction of the total elemental selenium present. A new method was developed to analyze for cyclooctaselenium (Se8) in both synthetic samples and selenium-impacted sediments. Despite some analytical limitations, this gas chromatography-mass spectrometry (GC-MS) method is the first GC-MS method developed to identify and quantify Se8 in sediments. Once this method was established, it was then applied to more complex systems: first, the identification of compounds in mixed selenium-sulfur melt solutions, and then the determination of SenSm in selenium-impacted sediments. Despite complications arising from pronounced fragmentation in the ion source, assignment of definitive molecular formulae to chromatographically-resolved peaks was possible for five compounds. Developing a fully quantitative method to obtain elemental ratio information can aid in the assignment of molecular formulae to chromatographically-resolved SeS-containing chromatographic peaks. Coupling the existing gas chromatography method to an inductively coupled plasma-mass spectrometer (ICP-MS) system should accomplish this. However, due to a number of complications, this was not completed successfully during the duration of this thesis project. High detection limits for sulfur, retention time discrepancies, and inconsistent injection results between the GC-MS and GC-ICP-MS system led to difficulties in comparing results between both analytical methods. Despite these limitations, GC-ICP-MS remains the most promising method for the identification and quantification of SenSm compounds in synthetic melt mixtures and selenium impacted sediments. Author Keywords: gas chromatography-mass spectrometry, sediments, selenium
Fate and Effects of Silver Nanoparticle Addition in a Lake Ecosystem
The potential release of nanoparticles into aquatic environments is raising global concerns. As antimicrobials, silver nanoparticles (AgNPs) are among the most prominent form in use. Despite this, their fate, long-term toxicity, and ecological relevance have yet to be investigated largely under natural settings with seasonality and environmental complexity. To better understand the environmental significance, we released AgNPs into Lake 222 at the Experimental Lakes Area over two years. AgNPs remained suspended in the water column and were detected throughout the lake and in the lower food web. Total Ag concentrations ranged from below 0.07 to 18.9 μg L-1 in lake water, and were highly dynamic seasonally both in the epilimnion and hypolimnion depending on the physical, chemical and biological conditions of the lake. Approximately 60% of the measured Ag mass in October was present in the sediment in 2014 and 50% in 2015 demonstrating relatively high sedimentation and removal from the water column. During winter months, Ag was largely absent in the water column under the ice. After ice melt and before summer stratification, Ag concentrations increased in the lake suggesting AgNPs may not be tightly bound to the sediment and are able re-enter the water column during spring mixing events. Despite temporal variation, total Ag was highly synchronous across spatial locations for both years, indicating rapid dispersal upon lake entry. When investigating AgNP sizes using spICPMS, size distributions were similar across spatial locations, with the 40-60 nm size class constituting approximately 60% of all particles identified. Large aggregates (>100 nm) and dissolved Ag were infrequently detected within the lake. Ag accumulated in the lower food web ranging from 0.27-16.82 μg Ag mg C-1 in the bacterioplankton and 0.17-6.45 μg Ag mg C-1 in algae (particulate fraction). Partial least squares models revealed the highest predictors of Ag accumulation were dissolved nutrients including DOC, TDN, TDP in bacterioplankton. Major predictors for particulate Ag included temperature, dissolved oxygen, and sampling date. The diversity of predictors among biological compartments emphasizes the importance of understanding the role of environmental complexity within the lower food web. Despite Ag accumulation we did not detect strong negative effects on the lake food web. An increase in particulate and bacterioplankton chlorophyll-a occurred after addition in contrast to reference lakes, which may indicate a hormetic response to low dose AgNP concentrations. Our findings provide the first whole-lake perspective regarding Ag fate and toxicity, suggesting small scale experiments may overestimate environmental responses. Author Keywords: Ecotoxicity, Fate, Lower food web, Silver Nanoparticles, Whole-lake addition
Equilibria and distribution models of ionizing organic chemical contaminants in environmental systems
Ionizing organic chemicals are recognized as constituting a large fraction of the organic chemicals of commerce. Many governments internationally are engaged in the time-consuming and expensive task of chemical risk assessment for the protection of human and environmental health. There are standard models that are consistently used to supplement experimental and monitoring data in such assessments of non-ionizing organics by both government regulators and industry stakeholders. No such standard models exist for ionizing organics. Equilibrium distribution models, the foundational equations within multimedia environmental fate models for non-ionizing organics, were developed for the standard series of biphasic systems: air-water, particle-water, air-particle and organic-aqueous phases within living tissue. Multiple chemical species due to the ionization reaction were considered for each system. It was confirmed that, under select conditions, the properties of the neutral parent are sufficient to predict the overall distribution of the organic chemical. Complications due to biotransformation and paucity of identifiable equilibrium distribution data for ionizing organics limited the development of the model for living tissues. However, the equilibrium distributions of ionizing organics within this biotic system were shown to correlate with the abiotic sediment-water system. This suggests that the model developed for particle-water systems should be adaptable to the biotic system as model input and test data become available. Observational data for soil- and sediment- water systems, i.e., particle-water systems, allowed the development of a primarily non-empirical distribution equation for mono-protic acids; this model was almost entirely theoretically derived. The theoretical approach to model development allowed a quantitative assessment of the role of the neutral ion pair, resulting from the complexation of the organic anion with metal cations. To demonstrate the model's potential usefulness in governmental screening risk assessments, it was applied to a broad range of mono-protic organics including drugs and pesticides using standard property estimation software and generic inputs. The order-of-magnitude agreement between prediction and observation typical of the existing models of non-ionizing organics was generally achieved for the chemicals tested. The model was sensitive to the octanol-water partition coefficient of the most populous species. No calibration set was used in the development of any of the models presented. Author Keywords: bioconcentration, chemical equilibrium, environmental modelling, ionizing organic, sorption
Investigating the sources and fate of monomethylmercury and dimethylmercury in the Arctic marine boundary layer and waters
Monomethylmercury (MMHg), the most bioavailable form of mercury (Hg) and a potent neurotoxin, is present at elevated concentrations in Arctic marine mammals posing serious health threats to the local populations relying on marine food for their subsistence living. The sources of MMHg in the Arctic Ocean surface water and the role of dimethylmercury (DMHg) as a source of MMHg remain unclear. The objective of this research was to determine the sources and fate of methylated Hg species (MMHg and DMHg) in the marine ecosystem by investigating processes controlling the presence of methylated Hg species in the Arctic Ocean marine boundary layer (MBL) and surface waters. A method based on solid phase adsorption on Bond Elut ENV was developed and successfully used for unprecedented measurement of methylated Hg species in the MBL in Hudson Bay (HB) and the Canadian Arctic Archipelago (CAA). MMHg and DMHg concentrations averaged 2.9 ± 3.6 (mean ± SD) and 3.8 ± 3.1 pg m-3, respectively, and varied significantly among sampling sites. MMHg in the MBL is suspected to be the product of marine DMHg degradation in the atmosphere. MMHg summer (June to September) atmospheric wet deposition rates were estimated to be 188 ± 117.5 ng m-2 and 37 ± 21.7 ng m-2 for HB and CAA, respectively, sustaining MMHg concentrations available for bio-magnification in the pelagic food web. The production and loss of methylated Hg species in surface waters was assessed using enriched stable isotope tracers. MMHg production in surface water was observed from methylation of inorganic Hg (Hg(II)) and, for the first time, from DMHg demethylation with experimentally derived rate constants of 0.92 ± 0.82 x 10-3 d-1 and 0.04 ± 0.02 d-1 respectively. DMHg demethyation rate constant (0.98 ± 0.51 d-1) was higher than that of MMHg (0.35 ± 0.25 d-1). Furthermore, relationships with environmental parameters suggest that methylated Hg species transformations in surface water are mainly biologically driven. We propose that in addition to Hg(II) methylation, the main processes controlling MMHg production in the Arctic Ocean surface waters are DMHg demethylation and deposition of atmospheric MMHg. These results are valuable for a better understanding of the cycle of methylated Hg in the Arctic marine environment. Author Keywords: Arctic Ocean, Atmosphere, Demethylation, Dimethylmercury, Methylation, Monomethylmercury

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