▼ The chronology of ancestral Lake Erie is poorly constrained. As the Laurentide Ice Sheet began to retreat to the northeast, a large proglacial lake formed named ancestral Lake Erie. Several studies have focused on the geomorphic relationships between lake stages and strandlines of ancestral Lake Erie, but the lake’s chronology and the sedimentology of its sediment are largely unknown. The objectives of this study is to use analysis of lacustrine sediment to determine the duration of ancestral Lake Erie above the Warren stage, test the existence of a low stand (Lake Ypsilanti), and map strandlines in northwest Ohio north of the Maumee River. Of the twelve mapped water planes in northwest Ohio using LIDAR data, seven have been mapped previously and five new water planes were found. Approximately 12 m of lacustrine sediment cores were collected from Stranahan Arboretum, Wildwood Metropark, and Oak Openings Metropark in Lucas County, Ohio. The glaciolacustrine sediment is rhythmically laminated, consisting of mostly alternating laminae of clay and silt. Of the counted rhythmites at each site, a maximum number of 507 is from Oak Openings Metropark. Magnetic susceptibility, loss on ignition, grain size analysis, and bioturbation data were used to interpret the rhythmites as varves. The lack of ravinement surfaces, pedogenesis, and/or a broad unconformity is used to negate the existence of the Lake Ypsilanti low stand. An important result of this study is that the ~500 years of sedimentation recorded by varves suggests that ancestral Lake Erie existed over a shorted time period than previous studies that relied on radiocarbon dating. Advisors/Committee Members: Fisher, Timothy.

▼ Polycyclic aromatic hydrocarbons (PAHs) are globally found contaminants, classified into two main groups: petrogenic and pyrogenic. Petrogenic PAHs are introduced naturally into the environment by oil seeps or anthropogenically by spills of crude or refined petroleum product. Pyrogenic PAHs are formed from the incomplete combustion of fossil fuel or biomass and are commonly distributed by atmospheric deposition and urban runoff. The persistence and toxicity of PAHs make them a target for remedial investigations. Otter Creek, northwest Ohio, is a small tributary to Maumee Bay and has been associated with natural oil and multiple incidents of crude/refined oil spills. As part of the greater Maumee River Area of Concern, PAH contamination has been documented, but never attributed to sources. Knowledge of PAH type may help in remedial actions planned for the creek. A modified EPA Method 8270 was used for the analysis of 23 Otter Creek sediment samples by gas chromatography/mass spectrometry (GC/MS). A suite of 44 non-alkylated and alkylated PAHs was identified and quantified in selected ion monitoring mode. PAH source allocation was accomplished through compilation of diagnostic data, including distribution histograms of homologous PAH series, key diagnostic ratios, and principal component analysis. Total PAH concentrations in Otter Creek ranged from 10.9 to 3015.0 mg kg-1. Sites located at the headwaters had relatively low concentrations compared with downstream sites associated with PAH point sources and were considered baseline values of PAH contamination. Pyrogenic PAHs associated with urban background were prevalent in the headwaters section of the creek. As proximity to known point sources increased, total PAH concentrations increased and sediments exhibited mixing of petrogenic and pyrogenic sources. Mixed signatures were predominant over the refinery and residential stretches of the creek. Furthest downstream, the industrial portion of Otter Creek contained the highest PAH concentrations and mainly petrogenic features. Advisors/Committee Members: Spongberg, Alison L.

▼ Steroid hormones are natural substances excreted by humans and livestock while synthetic steroid hormones are extensively used as growth promoters and contraceptives. Both have been widely detected in environmental matrices. These compounds enter environmental water bodies dissolved in effluent of municipal wastewater treatment plants or in runoff of animal waste from livestock operations. Batch equilibrium sorption studies of progesterone, melengestrol-acetate, estrone, 17β-estradiol, 17α-estradiol, 17α-ethinylestradiol and estriol on a sandy loam soil have been conducted. Results suggest that the mobility of estrone, 17β-estradiol, 17α-ethinylestradiol and estriol in this sandy loam soil would be low due to their strong sorption. Sorption of progesterone and melengestrol-acetate is stronger, thus mobility of these two would be even lower. However, estriol would be more mobile than any of the other hormones tested due to the low sorption to the tested soil. Degradation of progesterone and melengestrol-acetate in this soil was tested and gave half-lives of 1.06 and 1.94 days, respectively. The five hormones (17-α ethynylestradiol, 17α-estradiol, 17β-estradiol, estrone and estriol) with lower sorption are expected to degrade rapidly and be effectively removed from the system. In the high and low flow rate microcosms, progesterone, melengestrol-acetate, estrone, 17β-estradiol and estriol in effluent were below the detection limits throughout the experiment. Only 17α-ethinylestradiol and 17α-estradiol were detected in much lower concentrations in the effluent than at the input. Residuals of progesterone and melengestrol-acetate in soil columns from the microcosms showed that degradation dominated in the microcosm. Overall, the high flow rate tested in this study was favored due to its good removal efficiency and the higher performance. Advisors/Committee Members: Spongberg, Alison L.

▼ Eolian sand deposited in lakes downwind of coastal sand dunes record a history of paleoclimatic fluctuations. Studies from embayed lakes along the east-central coast of Lake Michigan indicate that peaks in eolian sand within lake sediments correspond to climatic, sunspot, and lake-level fluctuations. The hypothesis tested herein is that the eolian sand signals from sediment within the Grand Mere Lakes, MI, which are downwind of sand dunes along southeastern coastal Lake Michigan, record the same climate history and lake-level fluctuations observed along the east-central Lake Michigan coastline. Sediment cores were extracted from the Grand Mere Lakes in Berrien County, MI, and analyzed for variations in weight percentage of sand with depth, the sand signal, at 1-cm sampling intervals. Radiocarbon dates obtained from terrestrial macrofossils within the cores were used to develop an age-depth model, from which sedimentation rates were derived, both for the varying lithologies and the entire core. Spectral analyses of the sand signal data using both the multi-taper and REDFIT methods indicate multiple periodicities that correspond to those from other regional and global studies, including Lake Michigan lake-level fluctuations, Lake Michigan coastal dune formation, and solar cycles. The tested hypothesis is accepted, and the common periodicities between the Grand Mere Lakes sand data and other studies suggest that this new dataset is not random, and is best explained as a record of paleodune mobility. The dataset is a paleorecord of wind or storminess experienced in the southern Lake Michigan basin and beyond, from the mid to late Holocene, and thus may be an effective proxy for paleoclimate in the southern Lake Michigan basin. Advisors/Committee Members: Fisher, Timothy.

▼ Soil and plant samples were collected from a heavy metal contaminated site in Fostoria, located in northwest Ohio. Copper and lead are the primary metals found at high concentrations on site. The soil at the study site has minimal adsorption capacity and without plant accumulation, the metals would likely be leached offsite. Soil and plant samples were collected from mine sites in Houghton Co. Michigan for comparison with the Ohio site. The objectives of this study are 1) to determine the adsorption behavior of copper and lead in Fostoria; 2) evaluate the effects of pH and ionic strength on the adsorption of copper and lead; 3) determine the applicability of plants from Michigan mine sites to the Fostoria soil. Results indicate that adsorption capabilities in the Fostoria soil are low. Metals exist in the living and decaying tissue of plants on site and are adsorbed to the mineral and organic fractions of the soil. As ionic strength increased, adsorption decreased. pH variation in the soil had little effect in sorption of metal ions. It is important to maintain a plant cover that will sustain a constant level of metals in the A-Horizon due to leaching concerns. Stinging nettles, growing on the lagoon, are very effective at removing not only copper, but a suite of metals, from the soil and therefore are important in preventing leaching of heavy metals. Stinging nettles were found to be a potential hyperaccumulator of metals and since mine plants that were investigated did not sequester significant concentrations of metals and no hyperaccumulators were located at those sites, application of non-indigenous plants is not recommended at this time. Natural attenuation is the preferred method of remediation at the Fostoria site. Advisors/Committee Members: Spongberg, Alison L.

▼ Glacial stratigraphy from the Thunder Bay lowland, northwest Ontario, indicate glaciolacustrine deposition prior to and after a Superior Lobe advance. Rhythmites present below and above Superior Lobe diamicton indicate ~300 years of glaciolacustrine sedimentation prior to the advance and at least 160 years of glaciolacustrine sedimentation when the Superior Lobe was at the Marks Moraine. This varve chronology, coupled with new radiocarbon dates from northwest Ontario, indicate: i) the Rainy Lobe stood at the Brule Creek Moraine at ~10,200 14C yrs BP fronted by glacial Lake O’Connor in the western Thunder Bay lowland; ii) the Superior Lobe advanced westward into Lake O’Connor between ~9.9 and ~9.7 14C yrs BP; iii) glacial Lake Kaministiquia occupied the reentrant between the Marks and Dog Lake Moraines between ~9.7 and ~9.5 14C yrs BP; and iv) the Superior Lobe retreated from the Marks Moraine after ~9.5 14C yrs BP, fronted by a glacial lake. Advisors/Committee Members: Fisher, Timothy G.

▼ Recreational boating facilities have historically been areas of polycyclic aromatic hydrocarbon (PAH) contamination brought upon by a variety of sources including stormwater runoff, petroleum product combustion, atmospheric deposition, and fueling operations. These compounds can be released to the environment through disturbance of the sediments. Physicochemical reactions of particulate phase organic matter with organic contaminants in contaminated sediments are one of the factors that may influence the release of these contaminants to the surrounding environment. Relationships between these organic matter components and PAHs may be a deciding factor in determining the fate of these dredged sediments, including their possible re-use. In this study, the relationships between PAH concentrations and organic matter components are presented. Desorption kinetics are examined in a laboratory setting using Tenax® TA resin beads that act as an infinite sink for hydrocarbons. Three marinas, along the Western Basin of Lake Erie were chose to represent common marina settings throughout the basin. Samples were analyzed for organic matter, total organic carbon, black carbon, and PAHs. Concentrations of PAH compounds were variable within and between marinas. Ratios of PAH compounds indicated that most chemicals are from a pyrogenic origin. Although it was the smallest portion of the quantified organic matter, black carbon showed the best correlation to PAH concentrations. Desorption trials show compounds desorb in a biphasic component manner, a fast desorbing component and a slow more “refractory” component. Desorption kinetics were mostly related to the quality of organic matter present, with slow desorbing sites having higher black carbon quantities. Advisors/Committee Members: Spongberg, Alison.

▼ Cores from marshes along the southwest shore of Lake Erie were 210Pb age-dated and analyzed for heavy metal and pesticide pollutants. The North Marsh is directly affected by agricultural run-off, while the West Marsh has been diked since 1978. Since marshes can act as sinks for metal, pesticides, and suspended solids, the chemistries of the marshes were expected to differ. However, concentrations of Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn did not differ. Metal accumulation within each marsh was different for every metal studied except Ni. This was also true for accumulation averages from background (pre-1978) and recent deposits (1979-1997), which indicate the diking of the West Marsh has had a significant impact on the metal accumulation. Previously used pesticides, which have been banned for many years, were also found in both marshes. However, pesticide concentrations are higher in the agriculturally impacted marsh. Advisors/Committee Members: Spongberg, Alison L.

▼ Long-term collection of soil temperature with depth is important when studying climate change. The international program GLOBE® provides an excellent opportunity to collect such data, although currently endorsed temperature collection protocols need to be refined in order to enhance data quality. To do this, protocol based methodology and automated data logging, along with other physical data, where used to collect soil temperature to a depth of one meter. Data show that the diurnal and shallow variation ceases at around 50 cm depth. Therefore the need to incorporate deeper depths into the current protocols, for heat flux calculations is warranted. The manual methodology was also found to give representative data.In order to add to the current state of knowledge regarding occurrence and fate of Pharmaceutical and Personal Care Products (PPCP) in the environment, influent, effluent and biosolids from three wastewater treatment facilities in Northwest Ohio, USA, and a stream containing effluent discharge from a rural treatment facility were analyzed for PPCP compounds. The three WWTP facilities vary in their size and in the community served, but are all Class B facilities. One facility was sampled multiple times in order to assess variability. Twenty compounds including several classes of antibiotics, acidic pharmaceuticals, and prescribed medications were analyzed using ultrasonication extraction, SPE cleanup and liquid chromatography electrospray ionization tandem mass spectrometry. The highest number of compounds and the greatest concentrations were found in the influent from the largest and most industrial WWTP facility. Short-term temporal variability was minimal at this facility. Many compounds, such as clarithromycin, salicylic acid and gemfibrozil were found at concentrations more than one order of magnitude higher than found in the effluent samples. Effluent waters contained elevated levels of carbamazepine, clindamycin and sulfamethoxazole. Differences in composition and concentration of effluent waters between facilities existed. Biosolids samples from two different facilities were very similar in PPCP composition, although concentrations varied. Ciprofloxacin was found in biosolids at concentrations (up to 46 ug/kg dry mass) lower than values reported elsewhere. Diclofenac survived the WWTP process and was found to persist in stream water incorporating effluent discharge. The low variability within one plant, as compared to the variability found among different wastewater treatment plants locally and in the literature is likely due to differences in population, PPCP usage, plant operations and/or local environment. These data are presented here for comparison with this emerging set of environmental compounds of concern. Advisors/Committee Members: Spongberg, Alison.