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Two types of oily waste sludges generated by a railroad maintenance facility were studied to reduce the volume of hydrocarbon waste. The specific goals of this laboratory study were to evaluate rate and extent of microbial degradation, benefits of organism addition, role of biosurfactant, and dewatering properties. The oily waste sludges differed in characteristics and contained a mixture of water, motor oil, lubricating oil, and other petroleum products. Degradation was measured using COD, suspended solids, GC measurements of extractable material, and nonextractable material concentration. Biosurfactant production was characterized using surface tension and polysaccharide measurements. Degradation of ten percent waste oil showed that the removal in a 91 day experiment was 75 percent for COD and suspended solids, 98 percent for extractable oil, and negligible for non-extractable material. It was concluded that methylene chloride extraction could be used to estimate degradation potential of a hydrocarbon waste. Addition of organisms increased the rate and extent of degradation over 22 days, but did not provide any benefits over 91 days. Data suggested that microorganisms degraded simple compounds first, then produced biosurfactants. It was thought that the biosurfactants remained attached to the organism membrane and increased solubility, stimulating the degradation of difficult to degrade waste oil. After oil was degraded the biosurfactants became ineffective. The dewatering properties of 10 percent oily sludge deteriorated with the production of biosurfactant and improved after the surfactant was degraded due to changes in oil solubility. / Master of Science

There are thousands of subterranean coal fires in the world that, because of incomplete combustion, emit a wide variety of volatile and semivolatile organic compounds to the atmosphere, water, and soil at concentrations that could pose health risks to humans and wildlife. The main goals of this study were to (1) review methods that are used to characterize physical and chemical characteristics of coal-fire sites, (2) determine relationships between gas emissions and physical and chemical characteristics of coal-fire sites, using a combination of regression and multivariate statistical methods, and (3) determine the concentrations of volatile and semivolatile organic compounds in water and soil at two coal-fire sites in eastern Kentucky. More specifically: The objective of Chapter 1 was to review past works and list technologies used over time. Eight years of coal-fire collection technologies were reviewed. A variety of methods and technologies were identified. Qualitative and quantitative preferences were noted. The objective of Chapter 2 was to identify and list uncontrolled coal-fire variables. These variables include complete/incomplete combustion; fire temperature and size; distance to fire; relative humidity and moisture in the system; geology, geochemistry, and age of coal; condition of the mine, sampling time of day; sampling equipment differences; and human error. A secondary objective of this chapter was to determine which coal-fire gases have strong relationships by using the principal component analysis (PCA) software JMP. The strongest relationship was between CO and H2S. Temperature and CH4 were also important. This indicates that incomplete combustion and polynuclear aromatic hydrocarbon (PAH) formation are likely occurring, setting the stage for Chapter 3. The objective of Chapter 3 was to identify and define the extent of soil and water hydrocarbon contamination at the Truman Shepherd and Lotts Creek coal fires in eastern Kentucky. No groundwater contamination was detected at either location. Soil contamination was found at both, but was much higher at Lotts Creek, potentially because of sorption onto soil organic matter (which is reduced at Truman Shepherd by an excavation attempt) and other physicochemical mechanisms. Soil contamination was localized to relatively small areas around coal-fire vents. Based on the results, future studies should consider: Attempting to duplicate these results in other geologic regions Quantifying greenhouse gas emissions from coal fires to consider their contribution to climate change. Coal-fired power plants are regulated, but coal fires, which produce many more harmful gases, are not Determining the feasibility of an oxygen-injection system to engender more complete combustion, therefore possibly reducing harmful gases Determining the feasibility of electricity production from coal fires Adopting a consistent federal coal-fire policy

Contaminated sediments represent a common environmental problem because they can sequester large quantities of contaminants which can remain long after the source of pollution has been removed. From the sediment these hazardous compounds are released into the sediment porewater where it can partition into organisms in the sediment and bioaccumulate up the food web; leading to an ecological and human health concern. The objective of this work is to investigate an emerging option in contaminated sediment remediation; specifically an option for in-situ treatment known as active capping. Conventional capping uses clean sediment or sands to separate contaminated sediment from overlying water and biota. Active capping is the use of a sorptive amendment to such a cap to improve its effectiveness. This work focuses on granular materials as direct amendments to conventional caps including; granular activated carbon (GAC), iron/palladium amended GAC, alumina pillared clay, rice husk char, and organically modified clays. All materials were investigated in batch sorption tests of benzene, chlorobenzene, and naphthalene in DI water. Additionally porewaters from three sites were extruded and the concentrations of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were measured. At Manistique Harbor and Ottawa River PCBs were identified as the primary contaminant of concern while PAHs were the contaminant of concern at the Grand Calumet River. At these sites a solvent extraction method was used to analyze the sediment concentrations of the contaminants of concern. From the former batch tests activated carbon and a commercially available organoclay were chosen for further investigation. This includes PAHs in batch sorption tests using extruded sediment porewater to investigate matrix effects, and PCB sorption in distilled water. / text

Der Einfluss des Biofilms, der Inkrustation, der Fließgeschwindigkeit und der Wasserqualität auf die Freisetzung von PAK wurde in Batch-, Drehkolbenreaktorversuchen und an einem Rohrleitungssystem untersucht. Chlorung von tauchgeteerten Edelstahlcoupons mit Biofilm führten zu einer fast vollständigen Ablösung des Biofilms und einer Zunahme der Freisetzung von Fluoren, Phenanthren und Fluoranthen. Die PAK-Freisetzung von tauchgeteerten Edelstahlcou-pons in einer Lösung von Trinkwasser mit 0,1% Natriumazid als Hemmstoff der Atmungskette, der den Biofilm nicht ablöst, führten zu einer Zunahme aller untersuchten PAK in der gleichen Größenordnung wie ohne Bio-film. In chloriertem Teerleachat wurden unter der teilweisen Anwendung einer einfachen Methode der kontinu-ierlichen Extraktion folgende PAK-Derivate analysiert: Chloracenaphthen, 1-Chlorpyren, 9-Fluorenon, Anthron. Da Reaktionsprodukte von Phenanthren und Fluoranthen nicht gefunden werden konnten, wird eine Weiterreaktion zu 9-Fluorenon vorgeschlagen, die durch die Pechoberfläche katalysiert wird. Instationäre Korrosion und nicht vorhandener aerober Abbau sind die Gründe für eine PAK-Zunahme während Stagnationphasen. / The influence of biofilm, encrustation, flow velocity and water quality on the release of PAHs was investigated in batch, continuously flown reactor experiments and in a pipe rig system. Chlorination of coal-tar coated stainless steel slides with biofilm resulted in an almost complete removal of the biofilm and an increase of the release of fluorene, phenanthrene and fluoranthene. PAH release of coal-tar coated stainless steel slides exposed to a solution of drinking water with 0,1% sodium azide as an inhibitor of the respiratory chain which did not remove the biofilm led to an increase of all observed PAHs up to the same magnitude as without biofilm. In chlorinated coal-tar leachate the following derivatives were detected while partly utilizing an easy method for a continuously extrac-tion: chloroacenaphthene, 1-chloropyrene, 9-fluorenone, anthrone. While reaction products of phenanthrene and fluoranthene could not be found a further reaction to 9-fluorenone catalysed by the coal-tar surface is proposed. Instationary corrosion and no aerobic degradation are the reasons for PAH increase during stagnation periods.

Der Einfluss des Biofilms, der Inkrustation, der Fließgeschwindigkeit und der Wasserqualität auf die Freisetzung von PAK wurde in Batch-, Drehkolbenreaktorversuchen und an einem Rohrleitungssystem untersucht. Chlorung von tauchgeteerten Edelstahlcoupons mit Biofilm führten zu einer fast vollständigen Ablösung des Biofilms und einer Zunahme der Freisetzung von Fluoren, Phenanthren und Fluoranthen. Die PAK-Freisetzung von tauchgeteerten Edelstahlcou-pons in einer Lösung von Trinkwasser mit 0,1% Natriumazid als Hemmstoff der Atmungskette, der den Biofilm nicht ablöst, führten zu einer Zunahme aller untersuchten PAK in der gleichen Größenordnung wie ohne Bio-film. In chloriertem Teerleachat wurden unter der teilweisen Anwendung einer einfachen Methode der kontinu-ierlichen Extraktion folgende PAK-Derivate analysiert: Chloracenaphthen, 1-Chlorpyren, 9-Fluorenon, Anthron. Da Reaktionsprodukte von Phenanthren und Fluoranthen nicht gefunden werden konnten, wird eine Weiterreaktion zu 9-Fluorenon vorgeschlagen, die durch die Pechoberfläche katalysiert wird. Instationäre Korrosion und nicht vorhandener aerober Abbau sind die Gründe für eine PAK-Zunahme während Stagnationphasen. / The influence of biofilm, encrustation, flow velocity and water quality on the release of PAHs was investigated in batch, continuously flown reactor experiments and in a pipe rig system. Chlorination of coal-tar coated stainless steel slides with biofilm resulted in an almost complete removal of the biofilm and an increase of the release of fluorene, phenanthrene and fluoranthene. PAH release of coal-tar coated stainless steel slides exposed to a solution of drinking water with 0,1% sodium azide as an inhibitor of the respiratory chain which did not remove the biofilm led to an increase of all observed PAHs up to the same magnitude as without biofilm. In chlorinated coal-tar leachate the following derivatives were detected while partly utilizing an easy method for a continuously extrac-tion: chloroacenaphthene, 1-chloropyrene, 9-fluorenone, anthrone. While reaction products of phenanthrene and fluoranthene could not be found a further reaction to 9-fluorenone catalysed by the coal-tar surface is proposed. Instationary corrosion and no aerobic degradation are the reasons for PAH increase during stagnation periods.