Soil and groundwater at many existing and former industrial areas and disposal sites is contaminated by organic solvent compounds that were released into the environment. Organic solvent compounds are heavier than water. When they are released into the subsurface, they tend to adsorb onto the soils and cause the appearance of LNAPL (light nonaqueous phase liquid) and DNAPL (dense nonaqueous phase liquid) pool. The industrial petroleum hydrocarbons (e.g., methyl tertiary-butyl ether, MTBE and benzene) and chlorinated solvent (e.g., trichloroethylene, TCE) are among the most ubiquitous organic compounds found in subsurface contaminated environment. One cost-effective approach for the remediation of the chlorinated solvent and petroleum products contaminated aquifers is the installation of permeable reactive zones or barriers within aquifers. As contaminated groundwater moves through the emplaced reactive zones, the contaminants are removed, and uncontaminated groundwater emerges from the downgradient side of the reactive zones. The objectives of this study were developed to evaluate the feasibility of applying in-situ chemical oxidation (ISCO) barrier and in-situ slow polycolloid-releasing substrate (SPRS) biobarrier system on the control of petroleum hydrocarbons and chlorinated solvent plume in aquifer. In the ISCO barrier system, it contained oxidant-releasing materials, to release oxidants (e.g., persulfate) contacting with water for oxidating contaminants existed in groundwater. In this study, laboratory-scale fill-and-draw experiments were conducted to determine the compositions ratios of the oxidant-releasing materials and evaluate the persulfate release rates. Results indicate that the average persulfate-releasing rate of 7.26 mg S2O82-/d/g was obtained when the mass ratio of sodium persulfate/cement/sand/water was 1/1.4/0.24/0.7. The column study was conducted to evaluate the efficiency of in situ application of the developed ISCO barrier system on MTBE and benzene oxidation. Results from the column study indicate that approximately 86-92% of MTBE and 95-99% of benzene could be removed during the early persulfate-releasing stage (before 48 pore volumes of groundwater pumping). The removal efficiencies for MTBE and benzene dropped to approximately 40-56% and 85-93%, respectively, during the latter part of the releasing period due to the decreased persulfate-releasing rate. Results reveal that acetone, byproduct of MTBE, was observed and then further oxidized completely. Results suggest that the addition of ferrous ion would activate the persulfate oxidation. However, excess ferrous ion would compete with organic contaminants for persulfate, causing the decrease in contaminant oxidation rates. In the SPRS biobarrier system, the food preparation industry has tremendous experiences in producing stable oil-in-water (W/O, 50/50) emulsions with a uniformly small droplet size. Surfactant mixture (71 mg/L of SL and 72 /L of SG) blending with water could yield a stable and the optimal emulsion was considered the best. The small absolute value of the emulsion zeta potential reduces inter-particle repulsion, causing the emulsion droplets to stick to each other when they collided. Overtime, large masses of flocculated droplets can form which then clog the sediment pores. The results can be used to predict abiotic interactions and distribution of contaminant mass expected after SPRS injection, and thus provides a more accurate estimate of the mass of TCE removed due to enhanced biodegradation. The effect of TCE partitioning to the vegetable oil on contaminant migration rates can be approximated using a retardation factor approach, where 0.28 years through a 3 m barrier. In anaerobic microcosm experiments, result show that SPRS can be fermented to hydrogen and acetate could be used as a substrate to simulate reductive dehalorination. The apparent complete removal of nitrate and sulfate by SPRS addition was likely a major factor that promoted the complete reduction of TCE at later stages of this study. Results from the column experiment indicate that occurrence of anaerobic reductive dechlorination in the biobarrier system can be verified by: (1) the oil: water partition coefficients of dissolved TCE into vegetable oil were be used to predict abiotic interactions and distribution of contaminant mass expected after SPRS injection. (2) The SPRS can ferment to hydrogen and acetate could be used as a substrate to simulate reductive dechlorination. The proposed treatment scheme would be expected to provide a more cost-effective alternative to remediate other petroleum hydrocarbons and chlorinated solvents-contaminated aquifers. Experiments and operational parameters obtained from this study provide an example to design a passive barriers system for in-site remediation.

Sponge are primitive multi-cellular organisms. They are important sources of secondary metabolites. In the previous studies indicated that the sponges harbor stable symbiotic microbial consortia. The mechanisms for maintenance and transmission of microbial consortia to the next generations are still not fully understood. The sponge, Cinachyrella australinesis, was chosen to further investigate relationship of the symbiotic bacteria within to the host. Fluorescent in situ hybridization ¡]FISH¡^was employed with non-specific ¡]EUB338¡^and specific oligonucleotide probes for bacteria. The sponge was cryo-sectioned¡]1£gm¡^and hybridized with fluorescent probes. The distribution and ratios of the bacteria in the sponge agreed with those of previous studies indicating that the symbiotic bacteria of C. australiensis are stable and endosymbiotic in nature.

Experimental studies showed the feasibility of adding metallic catalysts and tetralin for the upgrade and increased recovery of heavy oil during the in situ combustion process. Further experimental studies also showed the applicability of in situ combustion as a viable method of upgrading and improving recovery of intermediate oils. Three successful experimental runs were performed with heavy oil from Mexico (10.1 degrees API gravity). The first run was the control run without the addition of tetralin or metallic catalysts; the second run used heavy oil premixed with 3 wt% tetralin and 500ppm nickel catalyst; and the third run was with heavy oil premixed with 3 wt% tetralin and 500ppm iron catalyst. For the three runs, the cell production pressure was kept constant at 300 psig. The combustion cell was placed in a vacuum jacket and set to a temperature of 60 degrees C. For the only successful run with the intermediate Texas oil (22.0 degrees API gravity), the production pressure was also kept constant at 300 psig but the vacuum jacket temperature was set to a reservoir temperature of 40oC. During the runs for both oils, samples of produced oils and combustion flue gases were collected at regular intervals for analysis. These analyses included determination of oil viscosity and density, oil recovery, combustion front velocity, and apparent H/C ratio. Experimental results for the intermediate oil run, the oil gravity increased by 6 points showing the upgrading effects of in situ combustion on intermediate oils. Also, the high average combustion temperatures observed during the run indicated that in situ combustion may be applicable to reservoirs of similar characteristics to the intermediate Texas oil reservoir. Heavy oil experimental run results indicated that the use of tetralin and metallic catalysts increase the average combustion front temperature from 484 degrees C to 501 degrees C for the run with nickel catalysts, and from 484 degrees C to 492 degrees C for the run with iron catalysts. These results also show an increase in produced oil recovery from 83% to 90% of oil initially in place for the nickel catalyst run, and 83% to 86% of oil initially in place for the iron catalyst run.

In many regions of the world, groundwater is contaminated with a high level of arsenic that must be treated before it can be safely used as drinking water. In situ immobilization of arsenic from groundwater within subsurface environment could have major advantages over the conventional above-ground chemical coagulation-precipitation treatment process. In this study, we develop a novel technique that can in situ emplace iron oxides onto the sand grain surface of porous media under mild chemical and temperature conditions. The technique involves sequential injections of a preconditioned ferrous iron solution and an oxidant solution and then orchestrate the advective-diffusive transport of the two reagents in porous media to create an overlapped reaction zone where ferrous iron is oxidized and precipitated on the sand grain surfaces. We demonstrate through bench-scale column tests the feasibility of using this technique to create a large-scale iron oxide-enriched reactive barrier in subsurface environment for in situ removal of arsenic. A sand filter with a fresh iron oxide coating can treat thousands of pore volumes of water contaminated with dozens of ppb arsenic before the coating needs to be regenerated. Arsenic breakthrough curves through the sand filter suggest that both reversible adsorption and irreversible precipitation are responsible for removing arsenic from the water. Unlike conventional excavate-and-fill permeable reactive barriers, the treatment capacity of our in situ created barrier can be in situ regenerated and replenished with a fresh coating.

Iron reduction is an important redox reaction in anaerobic environments for both biological and chemical cycling of elements such as carbon. However, the controls on the rate and extent of iron reduction are poorly understood and unlike other major terminal electron accepting processes, iron reduction has the added complexity that its oxidized form (ferric iron) exists primarily as one of several solid phases in environments with pH greater than 3. Thus, the distribution and form of ferric iron minerals are important controls on iron reduction in natural systems. For the first phase of this research a series of sequential chemical extractions was performed on a core taken from a landfill-leachate-contaminated wetland-aquifer system at the Norman Landfill, Norman, OK. The phases targeted by the sequential extractions consist of easily water soluble salts and ions present in the soil solution; weakly acid soluble iron (such as siderite and ankerite); easily reducible iron (such as ferrihydrite and lepidocrocite); moderately reducible iron (such as goethite, akageneite, and hematite); organically bound iron; magnetite; and pyrite. The second phase of this research involved creating in situ microcosm experiments that exposed native microbial communities to a test solution amended with 2-line ferrihydrite (Fe5HO8∙4H2O), electron donor (lactate and acetate), and a conservative tracer for a period of eleven days. The kinetics of iron reduction were then evaluated over time and the resulting changes in microbial community structure documented through DNA and RNA analysis. Results document the spatial distribution of iron phases at the contaminated wetland-aquifer interface. Results of the sequential extractions indicate that ferrihydrite was present throughout the core. Accordingly, ferrihydrite was used in subsequent experiments on in situ microcosms to evaluate the kinetic controls on the microbial reduction of ferrihydrite. The results of these experiments show that microbial communities actively responded to the introduction of the amended ferrihydrite solution by increasing their community size and reducing ferrihydrite to an iron (II) phase in increasing amounts over an eleven day period.

For precision agriculture to work, an automated process to collect spatial-variability data within a field is necessary. Otherwise, data collection is prohibitively expensive and time consuming. Furthermore, to minimize measurement error due to harvesting method, data-collection processes involving normal cotton harvesting and ginning operations must be used. For the case of cotton, an automated prototype system using image processing to measure the micronaire value of cotton fiber during harvest was designed and built in the laboratory. This system was tested with two image-processing algorithms to identify and remove the effects of objects present in the images that were not cotton fiber, and then measure the reflectivity in three Near-Infrared (NIR) wavebands. Both algorithms yielded similar results when used on seed cotton samples. The reflectivity measurement after removing the effects of foreign matter had a strong relationship to standard micronaire measurements (R^2= 0.73 and 0.74 for the ratio-image and single-image algorithms, respectively) with a root mean squared error (RMSE) of 0.28 and 0.27, respectively. The ratio-image pixel classification method classified an average of 58% of the pixels in an image as "cotton", while the single-image method classified an average of 81% of the pixels in each image as cotton. These results do not show as strong a relationship between micronaire and NIR reflectivity of cotton samples as previous research done with very uniform lint cotton calibration samples. This is attributed to the higher content of foreign matter in seed cotton samples. With higher trash cotton and fiber that has not yet been cleaned, results obviously are not as good as when using calibration cotton samples. These results indicate the system can be adapted to perform in-situ measurement of cotton fiber quality, specifically micronaire, and enable harvesters to create quality maps of a field automatically to allow better crop management.

In this field-scale study, air sparging (AS) system was applied at a petroleum-hydrocarbon spill site to remediate contaminated soil and groundwater in situ. The objective of this study was to evaluate the effectiveness of the AS system on volatile organic compounds (VOC) removal via the volatilization mechanism. Moreover, the AS system would also enhance the in situ bioremediation process due to the increased oxygen concentration in the subsurface. Results from the preliminary site characterization show that high concentrations of benzene and toluene were present in the subsurface in the western part of the site. Up to 15.62 and 30,957 mg/Kg of benzene and toluene were detected in soil samples, respectively. Moreover, up to 0.068 and 4.8 mg/L of benzene and toluene were observed in groundwater samples, respectively. The following remediation activities were conducted during the one-year investigation and remediation period: 1. Construction of four recovery wells were for light non-aqueous phase liquid (LNAPL) and contaminated groundwater extraction to prevent the expansion of VOC plume. The extracted groundwater was delivered to the wastewater treatment plant for treatment before discharge. 2. Installation of ten air sparging wells to enhance the removal of VOC through volatilization and biodegradation processes. 3. Conduction of (1) soil gas survey, (2) soil and groundwater sampling and analyses, and microbial enumeration periodically to evaluate the effectiveness of AS on VOC removal. Results from the field-scale study indicate that the AS system is able to effectively contain the plume. This can be confirmed by the following findings: (1) decrease in VOC concentrations in both soil and groundwater, (2) increase in carbon dioxide and increase in oxygen concentrations in the soil gas samples, and (3) increase in bacterial population in soil samples. Results from this study indicate that AS system can effectively contain the plume and manage this petroleum hydrocarbon spill site.

In der vorliegenden Arbeit wird erstmals ueber elektrochemische in situ Messungen zur Temperaturabhaengigkeit der Leitfaehigkeit von intrinsisch leitenden Polymeren berichtet. Die Leitfaehigkeit von metallischen Leitern nimmt mit der Temperatur ab. Dafuer sind die mit der Temperatur groesserwerdenden Phononenschwingungen im Festkoerper verantwortlich. Bei Halbleitern nimmt die Leitfaehigkeit mit steigender Temperatur zu, weil mehr Ladungstraeger freigesetzt werden. Die Leitfaehigkeit von intrinsisch leitenden Polymeren wird mit dem Polaron-/ Bipolaron-Modell erklaert, welches sich im wesentlichen auf Elemente des Halbleitermodells stuetzt. Daher wird auch bei intrinsisch leitenden Polyeren eine zunehmende Leitfaehigkeit mit steigender Temperatur erwartet. Die verschiedenen elektrochemischen Herstellungsverfahren, die sich in ihrem E-t-Verlauf unterscheiden, ergaben, dass man leitfaehiges Polyanilin nach allen drei Verfahren, jedoch mit unterschiedlicher Geschwindigkeit, erhaelt. Polyindolin bildet sich nur bei der potentiodynamischen Abscheidung in akzeptabler Qualitaet. Bei der potentiostatischen und der Potential-Sprung- Methode tritt offensichtlich schon waehrend der Herstellung die irreversible anodische Oxidation des Polymers auf. Die Messungen zur Zeitabhaengigkeit der Leitfaehigkeit, die als Grundlinie fuer die T-Abhaengigkeitsmessugen erforderlich waren, ergaben in allen Experimenten eine Abnahme der Leitfaehigkeit mit der Zeit. Bei Polyanilin nahmen die Leitfaehigkeiten bei den drei Herstellungsverfahren unter- schiedlich schnell ab. Bei Polyindolin scheint die zeitabhaengige Verlauf der Leitfaehigkeit vom Herstellungsverfahren unabhaengig zu sein. Bei Polyanilin und Polyindolin nimmt die Leitfaehigkeit mit der Temperatur zu. Der LF-T-Verlauf beschreibt dabei eine e-Funktion. Die Auswertung ergibt Aktivierungsenergien fuer die Freisetzung von Ladungstraegern, die im Bereich von 0,2 bis 0,5 eV liegen. Der Vergleich mit spektroskopischen Daten (UV-vis, IR) in der Literatur zeigt, dass zwischen 0,5 eV und 1,5 eV elektronische Uebergaenge beobachtet worden sind, deren Intensitaet mit zunehmender Leitfaehigkeit der Polymerfilme steigt, und die man deshalb als Aktivierungs- energien der Leitfaehigkeit interpretiert. Oberhalb einer bestimmten Temperatur (Polyanilin: 80 Grad C, Polyindolin: 65 Grad C) bricht die Leitfaehigkeit schnell zusammen. Dies ist auf einen thermischen Abbau des Polymers zurueckzufuehren. Bei beiden Polymeren veraendern sich die zyklischen Voltamogramme, die das Redoxverhalten der Polymere wiedergeben, ab den o.g. Temperaturen sprunghaft. Bei Polyanilin tritt ein neuer Peak auf, den ich als Oxidationspeak eines Abbauproduktes interpretiere. Eine genaue Identifizierung des Abbauproduktes ist mit den zur Verfuegung stehenden Methoden nicht moeglich gewesen.

Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references (leaves 168-176). Also available on the Internet.

Thesis (Ph. D.)--Rutgers University, 2009. / "Graduate Program in Microbiology and Molecular Genetics." Includes bibliographical references (p. 112-131).