This thesis covers the use of chemistry in the automotive industry with emphasis on environmental compliance via chemical reporting by database and internal Energy Dispersive X-ray Fluorescence (XRF) screening, third party laboratory material testing, and the future of the chemist in the United States (U.S.) automotive industry. The third party testing was performed at Western Kentucky University (WKU) via the Materials Characterization Center (MCC), Institute for Combustion Science and Environmental Technology (ICSET) Thermodynamics Laboratory, and using the Scanning Electron Microscope/Energy Dispersive X-ray Spectrometer (SEM/EDX) managed by the WKU Biotechnology Center. Furthermore, the tests conducted were used to investigate material defects, provide solid third party quantitative results to support our XRF screenings to ensure environmental compliance, and determine cost effective material replacements. The company for which the testing was performed and information obtained is involved with the production of electronics for many of the major automotive companies throughout the world. The company specializes in the production of wiring harnesses, electrical control units (ECU), boxes (junction, fuse, relay, etc), and electrical components. These four areas control everything from the vehicle's lights, CD/DVD player, and heater to windows, locks, and navigation system. The automotive industry is extremely competitive; therefore, each company must continually change and improve in order to survive. New materials are constantly required to meet the reduced costs implemented by the customer, as well as, improve the function and quality of the components, while maintaining compliance with global environmental standards.

Consumption of fish contaminated with mercury is the primary exposure pathway by which humans are exposed to mercury. Mercury is known to be a neurological toxin that can cause attention and language deficits, impaired memory, and impaired visual and motor function, especially in children under the age of six. In addition, mercury exposure can lead to other health problems in adults, such as damage to the kidney and increased risk of coronary heart disease. This study assesses the exposure to mercury through consumption of fish from Kentucky surface waters. The exposure assessment is based on data collected by the Kentucky Department for Environmental Protection (KDEP), Division of Water, from different streams and lakes in Kentucky and average consumption rates defined by the U.S. Environmental Protection Agency (EPA). The design of this study is established to determine if people in Kentucky are at risk of mercury contamination and whether the Kentucky fish advisory protects the population from this threat. The exposure analysis presented examines mercury in different fish species from different streams and lakes in Kentucky. Fillet samples of fish were examined by KDEP and the quantity of methylmercury was determined in micrograms per kilogram (ppm). These data were used to estimate the exposure under various scenarios for methylmercury. Exposure assessment is a major component of the risk assessment process and is used here to assess the magnitude of methylmercury contamination for people in Kentucky that consume fish. EPA has been determined the maximum contaminant level of mercury in fish to be 1 ppm, and stated that the general consumer should be advised to eat no more than 1 meal/week of noncommercial fish in the U.S. at this level. Also, they determined the reference dose of methylmercury to be 0.1 (J.g/kg of body weight/day. The result of categorizing Kentucky fishes according to EPA monthly risk-based fish consumption limits indicated that 22.8% of the fishes caught from lakes and 31.44% of the fishes from streams had a greater risk than the current Kentucky advisory would indicate. The calculated daily intakes of methylmercury have shown that the consumption of certain types of fish from lakes and streams will lead to ingestion of methylmercury that exceeds the acceptable level as determined by EPA.

Lead in soil has been shown to be a significant pathway of lead exposure in children. Several factors including age of housing units, exterior composition, and paint loading may affect the amount of lead present in the soil. The purpose of this study was to analyze soil lead levels on properties located in an historic district and relate those levels to the variables previously mentioned. A total of 30 soil samples were collected from housing units in a nationally recognized historic district. Concentrations of lead in the soil were analyzed using a NITON X-ray Fluorescence Spectrum Analyzer, following EPA Method 6200 and the instrument protocol. Significant differences were found between the soil lead levels and paint loading (fully painted vs. non-painted). Significant differences were also found between soil lead levels and exterior surface (frame, brick, and other). A correlation analysis revealed there was no correlation between housing age and soil lead levels. Soil lead can be used as a predictor of blood lead levels in children. Using the information regarding soil lead concentration, the relative risk of exposure to lead and the subsequent health effects can be estimated for children living in the study area. The results from this study can also be used to initiate other studies and develop educational strategies for the district.

This study examines the variation in the distribution of the concentration of atrazine, a triazine herbicide used in Kentucky to control weeds primarily in corn fields. Atrazine is known to have carcinogenic properties and is an endocrine disruptor in aquatic species even at low concentrations. Atrazine has the ability to be transported through the environment into water bodies due to its physical and chemical properties favoring its occurrence and distribution. Raw and Finished drinking water samples were collected from the Lewisburg water treatment plant which derives its drinking water supplies from a source water intake namely Spa Lake, which has a direct run-off from the fields with abundant atrazine application. Atrazine was analyzed in the collected water samples and was found in both the raw and finished drinking water in concentrations exceeding the Maximum Contaminant Level (MCL) of 3 ppb as established by the US Environmental Protection Agency (US E.P.A).The Safe Drinking Water Act (SDWA) methodology requires quarterly sampling strategy to be implemented by all small community water systems to monitor and control the concentrations of atrazine in finished drinking water. The presence of missing high concentrations of atrazine in finished water which are not measured in the regular quarterly sampling protocol is of concern for exposures and protection of public health and environment.

This study examines the transport of atrazine, an herbicide used in Kentucky to control grassy and broad-leaf weeds in corn fields, on suspended sediments. Atrazine is a known carcinogen and endocrine disruptor and has been shown to be toxic at low environmental concentrations. Atrazine has the capacity to adsorb to soil particles, which in karst areas such as those found in south central Kentucky can be transported directly into the groundwater. Suspended sediments and water were collected from a well at the Hawkins River in Mammoth Cave National Park during a spring storm and tested for atrazine. Atrazine was found in concentrations exceeding 3 |ig/l in all of the sediment samples collected. Concentrations of atrazine in the cave stream's water were low, ranging from nondetectable traces to 0.1 (j.g/1. These results indicate that, in some cases, adsorption to sediments may be a major mechanism for atrazine transport in karst regions. The relatively high levels of atrazine present on the suspended sediments raise serious concerns, since this mode of transport has received little attention in karst environments.

Congested roadways and declining air quality standards are major concerns for many communities faced with the challenges of suburban growth and city decay. How each community chooses to fight the problems created by urban sprawl depends greatly on individualized characteristics of the community. Analyzing and understanding unique values of each community provides a sound foundation for measures designed to promote sustainable growth initiatives. The Evansville, Indiana, region is experiencing many of the growing pains associated with increased residential, commercial, and industrial development. Many roadways are currently strained near capacity, and traffic problems are anticipated to increase over the next 20 years. Evansville was ranked 68 out of the 271 worst sprawling MPOs, and Vanderburgh County will be designated as "non-attainment" with the next EPA air quality ruling. This research demonstrates that the Evansville region has problems with urban sprawl, air quality, and roadway congestion. Local air quality data, roadway congestion, employer and employee surveys, and commute patterns are all analyzed to determine the existing characteristics of the community. As a means to mitigate current and future concerns, Travel Demand Management (TDM) strategies such as park and ride facilities should be utilized. Implementing shared used park and ride facilities will provide an effective and relatively inexpensive method of congestion reduction by providing motorists with a different commute option.

The Mammoth Cave System of south central Kentucky encompasses more than 560 km of surveyed cave passages. The largest groundwater basin (244 km2) found within this cave system emerges from the Turnhole Bend Spring on the Green River. During high flow conditions, water from this groundwater basin will spill over into the Echo River section of the cave. Previous research, including cave mapping and dye tracing (Quinlan and Ray, 1989; Currens and Ray, 1998; Coons, 1994), has delineated the boundaries of spring groundwater basins for numerous springs along the Green and Barren Rivers. These data showed that 60% of the water that flows through the Turnhole Bend Aquifer comes from beyond the boundaries and protection of Mammoth Cave National Park. This area outside the park is crossed by several major transportation routes, including Interstate 1-65, U.S. Highway 31 -W, and CSX Railroad. Because the Turnhole Bend Aquifer is crossed by these major transportation routes, the aquifer is vulnerable to contamination from accidental spills of hazardous materials. Dye tracing methods were utilized to better delineate the boundaries and sub-basins of the Turnhole Bend Groundwater Basin along Interstate Highway 1-65. The approximate boundaries developed by previous research by others were first used to located areas that had not been previously dye traced. Fluorescent dyes were used as tracers and were detected by both qualitative (yes/no) methods and by quantitative (discrete water sampling) methods. Data from quantitative dye traces performed during this research provided additional information on the behavior of water flow into and through the maturely karstified limestones found in the south central Kentucky karst. Dye traces performed during the wet season, late winter and spring, have shown that average flood pulse groundwater flow velocities often exceed 1 km/hr. These high flow rates are contrasted by flow rates in the order of 0.5 km/day during the summer when evapotranspiration is high and rainfall is less frequent. Data from the quantitative dye traces also indicate a significant difference in the residence times of the dye between the wet and dry seasons. Dye that was injected during the wet season had a relatively short residence time in the cave streams of approximately 2 to 3 days. Dry season quantitative dye traces are very different with residence times of over 12 days being recorded. This information is vital in determining the consequences of a sudden release of hazardous materials within the drainage basin of Mammoth Cave and demonstrates that emergency planning is crucial.

Biomonitoring has become an important component in bioassessment programs. It is used to maintain high water quality standards, and determine contaminant levels and biological affects in areas that have been heavily disturbed. The objectives of this research were 1) to improve and apply certain modern biomonitoring techniques and 2) to locate possible contaminant sources affecting the flora and fauna of the Green River and of Mammoth Cave. Actinonaias ligamentina (Lamarck, 1819), a freshwater mussel, was used for interpretation of these impacts as well as refinement of biomonitoring techniques. The mussels were collected in the Lawler Bend region of the Green River, an area upstream from the Mammoth Cave System, and from Haynes Shell Midden (dating 4000 - 6000 years before present) 45 miles downstream. Analyzing the shell nacre of these mussels, and the soft tissue of recently collected specimens, produced an abundance of information including high tissue concentrations of organochloride pesticides, significant concentrations of several metals including Cadmium, Copper, Mercury, Nickel, Silver and Zinc (with Mercury and Silver being found at the impact site), and numerous shell nacre stains. These results indicated possible impact from agriculture in the region and past and present contamination from local industries, and demonstrated the importance of the nacreous shell to biomonitoring programs.

Investigations of environmental hormone contamination commonly utilize solidphase extraction (SPE) followed by high-performance liquid chromatography / (electrospray ionization) tandem mass spectrometry (HPLC/(ESI)MS2) in the detection of estrogens. Matrix interference is widely reported. In this study, androgens were targeted alongside estrogens as environmentally co-introduced endocrine disrupting chemicals. Analytical methods were developed in parallel for detection of several hormones from each class, with comparison of protocols and instrumental parameters. Ultraperformance LC (UPLC®), an emerging technology advertised for reduced retention times, was used in place of HPLC for hormone separation. Applicability to diverse aqueous samples was tested. Matrix interference was combated with two rarely used techniques: atmospheric pressure chemical ionization (APCI) MS2 and extract purification by size exclusion chromatography (SEC). Infusion and spiking tests were performed in (ESI)MS2 and (APCI)MS2, demonstrating relative matrix disruption of hormone signals. An SEC fractionation protocol was developed and applied to extracted wastewater samples prior to UPLC/MS2 analysis. Hormone recoveries were compared to those obtained without SEC purification. In accordance with these experiments, it was found that estrogen and androgen contaminants can be simultaneously extracted using C18 SPE. This approach reduces the amount of sample, supplies, and time required in preparation for instrumental analysis. In UPLC separation, a broader gradient, slower flow rate, and increased run time were used for the androgens to counteract structural similarity and reduced polarity. The androgens were most readily detected using positive (ESI)MS2, versus negative for the estrogens, with modifier addition for signal enhancement. Electron delocalization in the estrogen and testosterone molecular structures facilitated ionization, permitting MS2 detection at or below 23 pg on-column versus 500 pg for the androgens lacking bond conjugation. Recoveries of all analytes from deionized water were 67-112% using UPLC/(ESI)MS2. Use of UPLC reduced retention times and solvent usage in comparison to HPLC, permitting adequate resolution of the hormones within 7 min in the presence of clean solvents. In environmental samples, the rapid analyses proved susceptible to matrix interference, with lack of signal resolution amidst unresolved complex mixtures. The application of (APCI)MS2 to complex samples showed promise in combating matrix interference, permitting detection of hormones spiked into wastewater that were not observed using (ESI)MS2. The ionization methods tended toward opposite matrix effects, with 140-410% recoveries (i.e. ion enhancement) from effluents using APCI and 5-120% (i.e. ion suppression) using ESI. Application of SEC prior to instrumental analysis removed some interfering compounds, allowing recoveries of 48-98% for several hormones using UPLC/(APCI)MS2.

No description available.