Doctor of Philosophy / Department of Agronomy / Gary M. Pierzynski / The bioavailability of Pb and Zn is linked to the solubility of solid phases and other soil chemical characteristics, which is associated with their environmental risk, suggesting that in situ stabilization of these elements can be accomplished by influencing their chemistry. However, more research is needed to investigate the effectiveness of different soil amendments on reducing Pb and Zn bioavailability. A lab study was conducted to evaluate the effects of five different P amendments and time on Pb/Zn speciation in a contaminated soil using synchrotron-based techniques, while a field investigation studied the effects of composted beef manure on plant biomass production and the influence on microbial function, size, and community shifts. In the lab study, the Pb-phosphate mineral plumbogummite was found as an intermediate phase of pyromorphite formation, which has not been documented until now. Additionally, all fluid and granular P sources were able to induce Pb-phosphate formation, but fluid phosphoric acid (PA) was the most effective with time and distance from the treatment. However, acidity from PA increased the prescence of soluble Zn species, which can have negative environmental consequences. Granular phosphate rock (PR) and triple super phosphate (TSP) reacted to generate both Pb- and Zn-phosphates, with TSP being more effective at greater distances than PR. In the field study, compost additions of 269 Mg ha[superscript]1 significantly decreased bioavailable Zn, while increasing estimated available water, plant nutrients, and plant biomass as compared to a contaminated control and low addition of compost (45 Mg ha[superscript]1) over three years. Additionally, compost additions of 269 Mg ha[superscript]1 significantly increased microbial enzyme activities, nitrification, and microbial biomass over the contaminated control through the duration of the study. Increases in microbial activity and biomass are related to increases in total C, available water, and extractable P, while negative relationships were found with electrical conductivity and with bioavailable Zn. The addition of lime or lime plus bentonite with compost did not further reduce metal availability, increase plant biomass, or improve the size or function of microbial communities. High compost additions caused a slight shift in microbial community structure according to phospholipids fatty acid analysis. Increases in the mole percents of both Gram-positive (Gm[superscript]+) and Gram negative (Gm[superscript]-) bacteria were found depending on site. Microbial biomass of Gm[superscript]+, Gm[superscript]-, and fungi were also increased by high compost additions. Results indicate that large additions of compost are needed to increase microbial biomass, improve microbial activity, and re-establish a healthy vegetative community. This study proposes that organic matter and P amendments can be used to stabilize and reduce the bioavailability of heavy metals in soils and mine waste materials, but must be managed carefully and intelligently.

Master of Science / Department of Biology / Craig Paukert / I evaluated sampling strategies and the effects of dike structure modifications in the lower Missouri River to better develop sampling and mitigation strategies to protect and enhance native river fishes. Sampling occurred in the lower 1,212 km of the Missouri River during October-June (coldwater season) and June-October (warmwater season) with stationary gill nets (GN), drifted trammel nets (TN), towed otter trawls (OT), and mini fyke nets (MF) from 2003-2006. We compared probabilities of detection (p), variability (coefficient of variation; CV) in catch per unit effort, and lengths for 25 species. Over 80% of adult large-bodied fishes were collected in GN during coldwater, >90% of chub spp. (Macrhybopsis) were collected in OT, and >90% of nine small-bodied and juvenile fishes were collected in MF. Trammel nets never had the highest p during coldwater, but had the highest or equally high p for 85% of adult large-bodied fishes during warmwater. Mean CV was lowest with GN for adult large-bodied fishes; chub spp. had the lowest CV in OT. Mean lengths were typically greater in GN and TN. Large river monitoring programs might best achieve the highest p, lowest variability, and widest size range of fishes by employing GN and OT during coldwater and TN, OT, and MF during warmwater sampling periods. We also compared fish community composition and the probability an un-notched and notched dike structure and channel sand bar (referred to as channel structures) was occupied by various fish species. Few differences in species richness and diversity were evident among channel structures. Notching a dike structure had no effect on proportional abundance for any habitat guild. Catch per unit effort (CPUE) was greater at notched dikes for only three (lake sturgeon Acipenser fulvescens, paddlefish Polyodon spathula, and shovelnose sturgeon Scaphirhynchus platorynchus) of 12 great river species. Occupancy at notched dikes increased for blue catfish Ictalurus furcatus and decreased for blue sucker Cycleptus elongatus, but did not differ for 17 (81%) other species. No distinct increase in occupancy at natural channel sand bars compared to engineered dike structures was evident. Mean CPUE was higher in dike structures than channel sand bars for four great river species (goldeye Hiodon alosoides, lake sturgeon, paddlefish, and shortnose gar Lepisosteus platostomus), but did not differ for ten. Our results suggest dike structures may provide necessary habitats for many fluvial species when compared to channel sand bars, but notching did not increase abundance or occupancy of most native Missouri River fishes.

Master of Arts / Department of Geography / John A. Harrington Jr / Environmental degradation is a major concern in agricultural landscapes. Innovative tools and methods will be necessary to identify and deal with the ongoing environmental impacts of past and present agricultural practices. The use of scenarios in environmental modeling is one way to address these concerns. Recently a group of researchers devised a framework for creating future land cover scenarios for two physiographic regions in Iowa. Based on that work, a suite of scenarios were created for Antelope Creek watershed in the Northern Flint Hills of Kansas. The Antelope Creek scenarios represent conditions pre Euro-American settlement, present day, increased intensification of agricultural production, enhancement of water quality, and enhancement of biodiversity. These scenarios were then modeled using the Soil and Water Assessment Tool (SWAT). Additional model runs were completed to compare SSURGO and STATSGO soil datasets. Results indicated that reductions in discharge, total suspended sediment and various nitrogen and phosphorus loads could be achieved by implementing modest changes to agricultural management practices. Results also indicated that a higher detail soil dataset such as SSURGO lead to slightly higher loads than with STATSGO data.

Master of Science / Department of Biological & Agricultural Engineering / Stacy L. Hutchinson / Soil erosion is a serious problem resulting in degradation of soil systems and nonpoint source (NPS) pollution of water resources. Concentrated overland flow is the primary transport mechanism for many NPS pollutants including soil, and locating areas where sheet flow transitions into concentrated flow is useful for assessing the potential for soil erosion. The ability to predict areas where overland flow transitions to concentrated flow and soil erosion potential is high assists land managers in implementing best management practices (BMPs) to reduce soil erosion and NPS. An erosion model, called the nLS model, was developed to identify transitional overland flow regions. The model is based on the kinematic wave overland flow theory and uses Manning’s n values, flow length, and slope as inputs to determine where overland flow transitions to sheet flow and soil erosion potential increases. Currently, the model has only been tested and validated for watersheds within Kansas. In order to assess model uncertainties and evaluate the model’s applicability to other regions, a sensitivity analysis on key input parameters was conducted. To assess model operations, several sensitivity analyses were performed on model inputs, including digital elevation models (DEMs) and landuse/landcover data (LULC). The impact of slope was assessed using two methods. First, by modifying the DEMs in a stepwise fashion from flatter to steeper terrains, and second, by modifying the elevation of each DEM cell based on the associated elevation error. To assess difficulties that might arise from the parameterization of surface roughness, LULC classes were assigned Manning’s n values within the suggested range using a Monte Carlo simulation. In addition, the critical threshold value used for locating erosion potential sites was modified, and alternative model calculations were used to assess the potential for improving model accuracy. Finally, the model was run using data from multiple sites, including two study areas in Hawaii and two in Kansas. The outputs for each site were analyzed in an attempt to identify any trends caused by site characteristics. Results from this study showed that the nLS model was sensitive to all of the inputs. Modifying the Manning’s roughness coefficient significantly altered the final nLS values and shifted the critical threshold points, especially in areas of the upper watershed. Changes in the slope value modified the nLS model outputs in a predictable manner, but there was some variability, especially in areas with lower slope values. In addition, discrepancies in the DEM, which may be present due to measurement or processing error, were shown to significantly alter the flow paths of a watershed. These findings suggest that accurate roughness coefficients and LULC data are especially important for regions with a steeper topography, and accurate elevation data is important for regions with lower slope values. The results also suggest that the threshold value for the model plays a vital role in locating potential soil erosion sites, and adjustments to this value could possibly be used as a method for calibrating the nLS model. Finally, the alternative model calculations used in this study did not significantly improve the accuracy of the nLS model, so the existing model is sufficient for obtaining accurate nLS estimates. The information gained from this study can improve the assessment of soil erosion processes due to concentrated overland flow. By successfully implementing a land management program that makes use of the nLS models, it should be possible to improve BMP placement and design, helping to improve water and soil quality.

The investigation of the atmospheric fate and transport of semi-volatile organic compounds (SOCs) often requires the sampling of large volumes of air (>100 m3) in a relatively short period of time. Conventionally high-volume pumps are not suitable for remote areas without access to reliable network power. We have developed a flow through sampler for such situations. It consists of a horizontally-oriented flow-tube, that can collect gaseous and particle-bound SOCs from large volumes of air by turning into the wind and having the wind blow through a porous sampling medium such as polyurethane foam. Through both indoor and outdoor experiments, we quantified its air sampling rate (through battery operated anemometers inside and outside of the flow tube), its sampling efficiency (by theoretical plate number analysis of the break-though curves for PCBs, PAHs, OCPs and PBDEs), and its accuracy (by comparison of concentrations, time trends, temperature dependences and isomer ratios with those obtained by conventional high-volume sampling) under conditions of constant and variable meteorological conditions (wind speed, temperature). The flow-through sampler was deployed to monitor SOC concentrations at a remote Chinese research station located close to Nam Co Lake, Tibet. During the campaign, fifteen 1 month-long samples were taken, corresponding to sample volumes between 5,000 and 20,000 m3. Despite those large sample volumes, only HCB and HCHs experienced break-through, but application of frontal chromatograph theory allows the estimation of breakthrough-corrected air concentrations even for those relatively volatile SOCs. The pesticide levels at Nam Co are generally very low. Most pesticides had higher levels during summer, resulting in a strong temperature dependence. This is correlated with air mass origin across the Himalayas in the Gangetic plains of India and Bangladesh. The flow through sampler constitutes a feasible method for reliably and quantitatively collecting SOCs from large air volumes.

Doctor of Philosophy / Department of Chemistry / Kenneth J. Klabunde / Solar energy driven catalytic systems have gained popularity in environmental remediation recently. Various photocatalytic systems have been reported in this regard and most of the photocatalysts are based on well-known semiconducting material, Titanium Dioxide, while some are based on other materials such as Silicon Dioxide and various Zeolites. However, in titania based photocatalysts, titania is actively involved in the catalytic mechanism by absorbing light and generating exitons. Because of this vast popularity of titania in the field of photocatalysis it is believed that photocatalysis mainly occurs via non-localized mechanisms and semiconductors are extremely important. Even though it is still rare, photocatalysis could be localized and possible without use of a semiconductor as well. Thus, to support localized photocatalytic systems, and to compare the activity to titania based systems, degradation of organic air pollutants by nanostructured silica, titania and mixed silica titania systems were studied. New materials were prepared using two different approaches, precipitation technique (xerogel) and aerogel preparation technique. The prepared xerogel samples were doped with both metal (silver) and non-metals (carbon and sulfur) and aerogel samples were loaded with Chromium, Cobalt and Vanadium separately, in order to achieve visible light photocatalytic activity. Characterization studies of the materials were carried out using Nova BET analysis, DR UV-vis spectrometry, powder X-ray diffraction, X-ray photoelectron Spectroscopy, FT-IR spectroscopy, Transmission Electron Microscopy, etc. Kinetics of the catalytic activities was studied using a Shimadzu GCMS-QP 5000 instrument using a closed glass reactor. All the experiments were carried out in gaseous phase using acetaldehyde as the model pollutant. Kinetic results suggest that chromium doped silica systems are good UV and visible light active photocatalysts. This is a good example for a localized photocatalytic activity. In contrast, our xerogel system shows comparatively high visible light photocatalytic activity for the titania based system, showing the importance of non-localized nature of photocatalysis. The Cobalt doped silica system shows interesting dark catalytic activity towards acetaldehyde and several other pollutants. Thus, in summary, based on the different activities we observed during our studies these materials could be successfully used to improve the quality of both indoor and outdoor air.

Doctor of Philosophy / Department of Biochemistry and Molecular Biophysics / Lawrence C. Davis / Synthetic dyes are capable of producing the whole color spectrum on account of their structural diversity but this diversity poses challenges in the degradation of dyeing wastes. Laccases and peroxidases from bacterial or fungal sources and parts of plants in the presence of hydrogen peroxide (H₂O₂) plus a mediator have been exploited in the bioremediation of synthetic dyes. However, intact plants have not found much favor despite their phytoremediation potential. The goal of this research was to further clarify ways by which whole plants bring about decolorization of different types of synthetic dyes. Hydroponically cultivated plants from two dicot families namely Arabidopsis thaliana and sunflowers (Helianthus annuus) were exposed to representative dyes from several classes: monoazo (Methyl Red and Methyl Orange), disazo (Trypan Blue, Evans Blue and Chicago Blue 6B), and arylmethane (Brilliant Blue G, Bromocresol Green, Malachite Green and Phenol Red). Tests were done in presence or absence of externally added H₂O₂, with or without a free radical mediator, 1-hydroxybenzotriazole, using UV-Visible spectrophotometry. The initial rate of decolorization and the overall percentage decolorization was calculated for each dye in the different treatments. Decolorization of the dyes from different classes varied between plant species and depending on the treatment. Except for Methyl Red, all dyes required added H₂O₂ as well as mediator to achieve rapid decolorization. Added H₂O₂ was found to be the limiting factor since it was degraded by plants within a few hours. Both species were able to slowly decolorize dyes upon daily addition of fresh dye even in the absence of added H₂O₂ and mediator, provided that nutrients were supplied to the plants with the dye. A. thaliana was found to be more effective in dye decolorization per gram tissue than sunflower when treated under similar conditions. Analysis of the residual dye solution by ESI/MS did not reveal any potential by-products following the decolorization treatment with plants, suggesting that the plant roots might be trapping the by-products of dye decolorization and preventing their release into the solution. All these findings support the potential application of whole plants for larger scale remediation.

Three different green technologies are compared in terms of net energy and carbon savings for a theoretical Toronto rooftop. Embodied energy values are calculated through Life Cycle Analysis and compared to the estimated energies produced and/or saved by each technology. Results show that solar photovoltaics displace the most carbon per m2 of roof space and solar thermal (for hot water) displaces the most energy. An in-depth analysis of an intensive green roof for growing food indicates that the high embodied energy of the materials is not quickly repaid by the sum of six energy savings that were examined (direct and indirect cooling, run-off treatment, transport of food, on-farm energy use, and activities that would otherwise be carried out). However, the energy and carbon benefits are not insignificant, but depend strongly on various assumptions. The methodology used is replicable and therefore useful for other locations.

Climate variability in the North Atlantic has been linked in part to the North Atlantic Oscillation (NAO). The NAO influences marine ecosystems in the northwestern Atlantic and the transport variability of the cold Labrador Current (LC). Understanding historic patterns and predicting future changes in LC transport require long-term and high-resolution climate records that are not available from instrumental data sets. This thesis presents the first century-scale sea surface temperature (SST)reconstructions from the Northwestern Atlantic using Mg/Ca ratios in the long-lived crustose coralline algae Clathromorphum compactum. which is characterized by a high Mg-calcite skeleton exhibiting annual growth increments. Results indicate strong correlations between interannual variations in Mg/Ca ratios and instrumental SST. The 131-year algal Mg/Ca record reveals NAO-type periodicities and evidence of past cold events and warming periods associated with basin-wide ecosystem shifts. Negative correlations between LC volume transport and algal Mg/Ca reflect the cooling influence of the LC on eastern Canadian shelf ecosystems.

Three different green technologies are compared in terms of net energy and carbon savings for a theoretical Toronto rooftop. Embodied energy values are calculated through Life Cycle Analysis and compared to the estimated energies produced and/or saved by each technology. Results show that solar photovoltaics displace the most carbon per m2 of roof space and solar thermal (for hot water) displaces the most energy. An in-depth analysis of an intensive green roof for growing food indicates that the high embodied energy of the materials is not quickly repaid by the sum of six energy savings that were examined (direct and indirect cooling, run-off treatment, transport of food, on-farm energy use, and activities that would otherwise be carried out). However, the energy and carbon benefits are not insignificant, but depend strongly on various assumptions. The methodology used is replicable and therefore useful for other locations.