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Included in this file is a CD drive titled "Chapter Three: Supporting Information" with a 00:40 second long animation. For best quality, view in VLC, not Quicktime Player. / <p>Groundwater contamination by dense non-aqueous phase liquids (DNAPLs ), such as chlorinated solvents, continues to be a significant environmental problem. When released to the subsurface, either due to improper disposal or accidental release, DNAPLs can form complex source zones whose geometry is largely controlled by the geological heterogeneity of the subsurface. These source zones are composed of disconnected, immobile blobs or ganglia trapped by capillary forces (referred to as DNAPL residual) between high-saturation regions located at permeability interfaces (referred to as DNAPL pools). The slow dissolution of DNAPL pools can result in the contamination of groundwater for time periods on the order of decades to centuries.</p> <p>The common conceptual model used in the investigation of DNAPL-contaminated sites is based primarily on the mass transfer from DNAPL to the surrounding aqueous phase in the saturated zone. However, the presence of a discontinuous gas phase above a DNAPL pool can significantly affect the mass transfer from the pool through repeated, spontaneous expansion and mobilization of the gas phase. This mechanism has not been included in the common conceptual models.</p> <p>The goal of this research was to develop a quantitative understanding of discontinuous gas phase expansion and mobilization above a DNAPL pool. This goal was addressed using a combination of small-scale and intermediate-scale laboratory experiments. Small-scale, no-flow vial experiments were used to measure the expansion of single gas bubbles above DNAPL pools, and provide the basis for the development of an analytical model to assess the effect of expansion by multi-component partitioning on the mass transfer from DNAPL pools. Small-scale flow cell experiments were used to measure spontaneous expansion rates in porous media, and provide visual data concerning the distribution of the gas phase. Small-scale air injection experiments were used to characterize the gas flow. Finally, an intermediate-scale flow cell experiment was used to provide larger-scale data concerning the transient distribution of the gas phase, and measure the effect of spontaneous expansion and mobilization on the aqueous-phase DNAPL constituent concentrations.</p> <p>The combined results of these experiments established a detailed conceptual model for the spontaneous expansion and mobilization of a discontinuous gas phase above a DNAPL pool. In this conceptual model, spontaneous expansion of a discontinuous gas phase above a DNAPL pool occurs due to multi-component partitioning, and depends on the concentrations of both the volatile DNAPL and the other dissolved gases. This expansion is more likely to occur, and will be faster, in shallower systems (i.e. lower hydrostatic pressures) containing coarser media (i.e. lower capillary pressures), more volatile DNAPL, and higher concentrations of other dissolved gases (i.e. higher partial pressures). Mobilization of the expanding gas will occur as discontinuous gas flow in most sands, where the repeated trapping and coalescence of gas clusters can allow rapid, large-scale vertical transport of the gas phase. This discontinuous gas flow can produce macroscopic gas fingers composed of multiple, discrete gas clusters. These macroscopic fingers can reach substantial heights above the pool surface, but the growth occurs predominantly at the pool's leading edge due to the stripping of other dissolved gases. This expansion and mobilization can significantly affect the mass transfer from the DNAPL pool if the gas phase is in direct contact with the pool surface; or if the gas phase is close to the pool surface, covers a large fraction of the pool, and the groundwater flow is sufficiently slow. The partitioning of DNAPL constituent from the mobilized gas phase to the aqueous phase well above the pool surface can also change the spatial distribution of aqueous-phase DNAPL constituent concentrations, increasing them above those that are expected based on theoretical calculations for strictly DNAPL-water systems, even at elevations where the concentrations are expected to be zero. The increased concentrations well above the pool surface can appear as short-duration events in the presence of a sustained gas phase, due to the partitioning of DNAPL constituents from the gas to the aqueous phase during multi-component mass transfer. The results of this research provide the necessary basis to begin incorporating this fundamental mechanism into the conceptual and mathematical models used for DNAPL-related research, the investigation ofDNAPL-contaminated sites, and the design and application of DNAPL remediation technologies.</p> / Thesis / Doctor of Philosophy (PhD)

The Deepwater Horizon (DWH) blowout, in the Gulf of Mexico, heavily contaminated miles of sandy beaches. Previous experience of petroleum contamination has shown that oil residues can persist in the sediments for decades. Biodegradation is the major mechanism of remediation regarding petroleum hydrocarbons. There is an urgent need to evaluate the competent indigenous microbial biomass in contaminated sediments if the risks posed by toxic oil residues, for the coastal ecosystem, are to be minimized. We report a field investigation during December 2010 and January 2011 regarding measurement of microbial activity in a sandy beach at the Bon Secour National Wildlife Refuge in Alabama. One transect of wells for sampling was installed in the beach; starting with multiport one, being most landward and thought to be least exposed to oil residue and ending with multiport four being the most seaward and exposed to the open waters of the Gulf of Mexico. Sediment samples were collected from different depths purposely chosen from above, inside, and below the oil layers for microbial analysis. Dissolved oxygen (DO) measurements were obtained and temperature was recorded while collecting the oxygen measurements. Pore water samples were collected for nutrient content and were monitored using the multiport sampling wells. Moisture content was analyzed from the sediments extracted at various depths at each well. pH and salinity were also analyzed for their contributing affect on the microbial community. Grain size distribution analyses were conducted on samples collected at all wells and at multiple depths to characterize the field study location. Results show that the bacterial biomass, as measured by Adenosine-5-triphosphate (ATP) and numbers of alkane and polycyclic aromatic hydrocarbon (PAH) degraders determined by Most Probable Number (MPN), are consistently higher in the sediment layers where oil had been detected. A very good correlation was observed among the relative abundance of bacteria in the different samples using MPN and ATP measurements. As expected, ATP based estimates of the microbial populations were two orders of magnitude higher than the alkane and PAH numbers determined by MPN, which reflect the non-cultivability of most environmental bacteria. The lower concentrations of PAH degraders than alkane degraders that were observed in this study are consistent with other studies, even though both populations are lower than in studies involving fresh oil trapped in beach or wetland sediments. PAHs (aromatics) are notoriously more resistant to biodegradation than alkanes, therefore allowing a lower number of biomass to grow using them. The overall smaller size of the bacterial numbers could be explained by the naturally occurring low-organic content of beach sand. On the other hand, this may be due to the highly weathered nature of the oil or it could reflect some other limitation. / Civil Engineering

The role of aquifer microorganisms in controlling arsenic contamination of Bangladesh aquifers via oxidation of organic carbon coupled with reduction of sedimentary iron oxyhydroxides and concomitant arsenic dissolution is generally accepted. What remains to be ascertained is the in situ biogeochemical mechanisms of cycling different carbon sources and directly relating indigenous microbiota to arsenic release. Using biomarker fingerprint approaches, this dissertation expanded the presently growing research in the biogeochemical carbon cycling controlling arsenic contamination in Bangladesh aquifers. Comprehensive profiles of microbial cell membrane components (PLFA and sterols) at three different aquifers tested the regional distribution of aquifer microbial community abundance, structure, and organic input potential across Araihazar. The highly variable bulk viable microbial biomass observed across these three sites confer both regional-scale and localized heterogeneous distributions of in-aquifer microbial communities which control carbon cycling in the aquifer. The lack of correlation between PLFA biomarkers and dissolved arsenic challenges the assumption that greater extent of microbial community metabolism results in an increase in arsenic in groundwater. Natural abundance radiocarbon isotope Δ14C analysis of cell membrane PLFA and available carbon pools (SOC, DOC, DIC) confirmed that young organic carbon substrates are being cycled at two of the three sites investigated here. This corroborates previous reports at nearby sites (Site B and F) thereby contributing to a well-constrained carbon source which actively support microbial metabolism over a regional scale. Sterol biomarker distributions were characterized to determine potential sources of organic input into the aquifer. In particular, the importance of raw human and/or animal sewage waste as a source of labile carbon was assessed by measuring the faecal biomarker Coprostanol and comparing its abundance to other sources of biogenic sterols using sewage input proxies (Sewage Contamination Index, Coprostanol/Cholesterol ratio). This was motivated by previous findings which correlated sewage contamination with dissolved arsenic at depth at nearby sites. While sewage contamination was low in the shallow aquifers at these sites, it is more likely that plant organic matter supported the elevated microbial abundance at shallow depths. On the other hand, evidence presented in this project suggests that sewage contamination intrudes into deeper aquifers (e.g. buried Pleistocene) and contributes to the vulnerability of previous pristine aquifers to future arsenic contamination. / Thesis / Master of Science (MSc)

The effects of contaminated supply air on the performance of a laminar proportional amplifier were experimentally investigated. The air supply was contaminated with oil vapor and particulate matter. Characteristic gain curves were obtained after each stage of contamination for various loading conditions. Photographs showing the location of contaminant deposits were taken. Two inlet geometries were studied: right-angle and straightthrough. The effects of maintaining a constant pressure and constant flow rate at the inlet throughout the duration of the tests were studied. Also, aspect ratio effects. were studied. Rapid deterioration of performance was evident with the right-angle entry due to inlet blockage. By milling a cavity in the bottom cover plate, the detrimental effects of inlet blockage were delayed. With constant pressure inlet conditions and straight-through geometry, significant buildup occurred in the nozzle region and downstream. Decrease in pressure recovery was linear with time. It was determined that null shift was caused by asymmetric buildup in either the nozzle region or splitter region. With constant flow inlet conditions, the damaging effects on performance were delayed for both inlet geometries. Also, for the straight-through inlet, the nozzle region was relatively clean when compared with the constant pressure inlet case. Null shift was found to be the result of asymmetric buildup in the downstream region. At lower aspect ratios, the damaging effects of contamination were more severe and occurred in less time. / Master of Science

There is emerging concern about the potential for elevated lead in water after water utilities conduct EPA mandated (or voluntary) partial replacements of existing lead service lines. Connections between dissimilar metals results in the accelerated corrosion of the less noble metal via galvanic attack, increasing metal concentrations in water and posing potential public health risks. Many practical problems associated with stopping galvanic attack between copper:galvanized iron and copper:lead via use of dielectrics have also been raised. Galvanic corrosion can be effectively stopped by isolating the dissimilar metals; however, completely eliminating electrical continuity may not always be practical or allowed by code. Instead, increasing separation distance between the two metals was hypothesized to considerably reduce galvanic corrosion. Galvanic corrosion and lead leaching were evaluated for lead:copper connections with varying separation distances while maintaining electrical continuity. Increased distance between lead and copper pipe dramatically reduced the galvanic current and the magnitude of lead release. Galvanized iron and copper connections were also investigated using various commercial fittings, and results verified that a controlling factor was separation distance between the two dissimilar metals. When considering the long-term behavior of partially replaced lead service lines, detrimental effects from galvanic corrosion worsened with time. Even when water was sampled consistently at moderate flow rate, the condition representing traditional partial service line replacement was 40% worse than a full lead service line. At elevated flowrates, lead concentrations and variability increased for partly replaced lead pipe versus full lead pipe due to reservoirs of lead rust formed via galvanic corrosion. At low flowrates, these negative impacts were not observed. Finally, crevices formed by the use of commercial couplings increased lead release. Overall, the results enhance practical understanding of galvanic corrosion impacts and use of dielectrics in water service lines and premise plumbing. / Master of Science

In many drinking water systems in the United States, disinfectant is added to water as it leaves the plant to maintain a residual concentration in the distribution system. The disinfectant residual is maintained to inactivate contamination that enters the distribution system, to control biofilms, and to act as a sentinel for contamination in the distribution system. A model was developed to evaluate the potential effectiveness of the disinfectant residual at inactivating contamination. The model was used to examine contamination of a hypothetical distribution system through backpressure at a cross-connection under different operating conditions. The dilution and pathway of the hypothetical contaminant were examined as the contaminant moved through the system. Disinfection and inactivation kinetic relationships were used to model the inactivation of the contaminant in the system by the amount of disinfectant present. The model showed that both chlorine and chloramines in each decay and inactivation condition considered provided some benefit over no disinfectant at all when examining susceptible organisms. Chlorine, under medium and low decay conditions, provided the best inactivation. Where 29.8% of total node time steps received a contamination of concern in the absence of disinfectant residual, as low as 4.8% of total node time steps received a contamination of concern in the presence of disinfectant residual. Chloramines was found to persist longer in the distribution system, but resulted in much lower inactivation compared to chlorine. Disinfectant doses typical of common distribution system operation were able to reduce the impact of contamination once it entered the distribution system but, except for four cases, were unable to prevent contamination from spreading within the distribution system. Therefore, it was concluded that presence of a disinfectant residual will reduce the total number of exposure opportunities from a contamination event, but cannot be relied upon to eliminate the chance of exposure resulting from contamination. / Master of Science

Creosote, containing many high molecular weight hydrophobic polycyclic aromatic hydrocarbons (PAH's), is present in the subsurface environment at the Oneida Tie-Yard in Oneida, Tennessee. Phytoremediation using hybrid poplar trees was chosen as the remedial technology on-site. Since monitoring began, the contaminant plume has been shrinking consistently and evidence has shown that remediation is taking place. However, remediation may be rate-limited by the desorption and dissolution kinetics of the PAH's on-site. The objectives of this research are to: (1) estimate the desorption and dissolution rates of 10 PAH's found in the subsurface and (2) estimate the amount of each PAH and total mass of contaminant that is irreversibly sorbed to the soil. Three laboratory desorption and dissolution experiments were performed using contaminated soil samples from the Oneida Tie-Yard site. The first experiment was a batch desorption equilibrium experiment, the second was a batch desorption kinetics experiment, and the third was a soil column dissolution kinetics experiment. The target compounds in this study were: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, and benzo(b)fluoranthene. The resulting data for the desorption equilibrium experiment revealed that rates of equilibrium were truly not instantaneous in the systems studied. However, because approximately 76% of PAH's desorbed by the first sampling event (3 days), an equilibrium isotherm was considered appropriate. Results showed that there is a sorbed reversible concentration that readily desorbs to the aqueous phase for each PAH. Additionally, it was determined that the percent removal of sorbed PAH's decreases with increasing molecular weight. Desorption curves based on experimental data were found to exhibit linear behavior over large variations in aqueous concentration, but showed exponential behavior as concentrations approached zero. Freundlich sorption equilibrium isotherms for the 10 monitored PAH's on-site were generally found to have N coefficient values over 1, especially over large variations in solution phase concentration, indicating a non-uniform sorbent. Dissolution of resistant PAH's under field-like conditions was determined to occur over long periods of time. Dissolution rates calculated from experimental data were shown to generally decrease with increasing molecular weight. Overall, desorption and dissolution kinetics of PAH's were shown to be rate-limiting factors to remediation at the Oneida Tie-Yard. / Master of Science

Poor sanitation infrastructure in rural areas can often lead to high levels of fecal contamination in local waterbodies and subsequent exposure to waterborne disease can occur. Although standard water quality measures such as quantification of E. coli can reveal relative concentrations of fecal contamination, they do not pinpoint the sources of such contamination. Source assessment in rural areas affected by untreated household waste might be improved with the human-specific, microbial source tracking marker HF183. This study attempted to quantify HF183 in two particular Appalachia streams with known discharges of untreated household waste. Water samples were taken above and at multiple points below these discharges on 29 occasions between August 2012 and April 2016, and tested for both HF183 and E. coli. HF183 was detected consistently in one of the study streams, though the concentrations were generally much lower than those previously reported in raw sewage; in the other watershed, HF183 was never detected. Further analysis via a multiple linear regression model showed a positive correlation between the level of E. coli and the proximity and number of known waste discharge points upstream from each sampling site. Primary conclusions of this study include: 1) HF183 is not always detected, even in watersheds with known sources of human fecal contamination, 2) it may be a useful water quality assessment tool where such contamination is suspected, particularly in cases where contaminant source allocation is necessary for setting mitigation priorities. / Master of Science

A <i>Pseudomonas</i> sp. capable of degrading tertiary butyl alcohol (TBA) as a sole carbon source, was isolated from a groundwater aquifer (50 ft. deep) at a petroleum refinery. The most probable number (MPN) of TBA degrading microorganisms was 4.9 x 10³ organisms/g (dry wt) of subsurface soil. Pristine subsurface soils, which did not have a history of petroleum contamination, had MPNs of < 2 TBA degrading organisms/g (dry wt) indicating a natural enrichment process at the refinery site. The Q_O2 of <i>Pseudomonas</i> sp. was 4.2 ml O₂/mg dry wt/h when TBA was the substrate. The optimum pH for growth was 7.0. The organism grew faster in continuous culture when TBA was the sole carbon source with a doubling time 33.6 h. The doubling time in batch culture was 112.3 h. When yeast extract was added to a mineral salts + TBA medium to concentrations greater than 1 mg/ml, TBA degradation was inhibited. When the yeast extract concentration was 0.1 mg/ml, a diauxy effect was seen in the growth rate. This suggested that TBA degradation by <i>Pseudomonas</i> sp. was subject to a regulatory mechanism. / M.S.