Barium sulfate scaling can cause many oilfield problems leading to loss of well productivity and well abandonment. Currently, diethylene triamine pentaacetic acid (DTPA) is used, along with synergist oxalic acid and potassium hydroxide, to remove the scale by dissolution. However, the chemical factors affecting this reaction are not known fully, leading to mixed results in terms of treatment effectiveness. This thesis investigates the effect of these factors, by analyzing the change in barite dissolution due to intrinsic factors like variations in formulation composition and extrinsic factors like presence of competing ions. The dissolution reaction is carried out, by taking the barite powder and chelant solution in a teflon round bottom flask and measuring the barite dissolved periodically, with an ICP-OES. The effect of different factors is studied by varying each factor individually and plotting the changes in solubilities. These lab tests show that solubility of barite (0.01mM in water), ideally, increases with increasing concentrations of chelating agents, even going as high as 239 mM. However experimental or field constraints lead to significant decrease in dissolution, especially at higher chelant concentrations. Thus, field tests to determine most effective chelant concentrations must precede treatment design. Lab tests also show that combination of DTPA with weaker chelating agents like ethylene diamine tetraacetic acid (EDTA), L-glutamic acid, N,N-diacetic acid (GLDA) or methyl glycine diacetic acid (MGDA) reduces barite dissolution and should be avoided during treatment design. Addition of synergists to the formulations, initially improves dissolution performance, especially for moderate chelant concentrations, but proves detrimental and hence must be avoided, over longer treatments. Finally, presence of competing ions in seawater, calcium sulfate and calcium carbonate, can significantly reduce barite dissolution and must be carefully studied for each formation-fluid system before design of treatments. Thus, this project sets a framework to identify the best chelant formulation and estimate its dissolution profile to ensure, a more informed treatment design for barite scale removal.

Previous studies on the effects of land cover influence on stream nitrogen have focused on base flow conditions or were conducted specifically within urbanized or primarily agricultural watersheds. While these studies have shown relationships between land cover and nitrogen, this relationship and the scale of influence could change during storms. The purpose of my study was to understand how land cover influences nitrogen in streams during storms. This was address using nine watersheds within the Little Tennessee Basin in North Carolina. While this basin is primarily forested, the nine watersheds have mixed agricultural, built, and forest land cover. Land cover influences were addressed through nitrogen concentration/discharge patterns, nitrogen concentration relationship to land cover, and comparison of storm and base flow nitrogen concentrations over time. Weekly base flow samples and samples from six storm were collected in 2010-2011. Total dissolved nitrogen (TDN), nitrate (NO??), dissolved organic nitrogen (DON), and ammonium (NH?⁺) concentrations were compared among sites. During most storms, DON peaked before the peak of the discharge while NO?? peaked after the peak of the storm. This suggest that DON could be coming from a near stream source or surface runoff while NO?? could be from longer pathways such as subsurface flow or from sources further away on the watershed. NO?? concentration varied among sites, while DON concentration varied more between base flow and storm samples. Examining the different landscape scales from 200-m local corridor, 200-m stream corridor, and entire watershed, watershed land cover was the best predictor for all the nitrogen concentrations. Agricultural and built combined best predicted TDN and NO??, while agricultural land cover was a better predictor of DON. For storms, nitrogen concentrations did not show seasonal patterns but was more related to discharge. Nitrogen concentration increased with discharge during storms and the more intense and longer storms had higher TDN and NO?? concentrations. However, conflicting seasonal trends were seen in monthly base flow. The more forested watersheds had high NO?? during the summer and low NO?? in the winter. For sites with higher NO??, the seasonality was reversed, with higher winter NO?? concentration. The least forested site had relatively constant nitrogen through the year at base flow and concentration decreased for most storms. Further studies on storms and nitrogen transport are needed to understand better the seasonal patterns of nitrogen input during storms. / Master of Science

At present, there are 41 elementary schools in Penghu County. There are at least 24 elementary schools with less than 100 students; this includes 10 small-scale schools with less than 50 students. It shows that the small-scale schools are the characteristics of the elementary school structure in Penghu County. During the past 10 years, 4 elementary schools have dissolved as there are insufficient students. The objective of this research is to discuss on current reuse policy for the reuse of school land and building. This research uses qualitative research method with conducting the in-depth interview to understand the reuse policy and the current community participation for the dissolved small-scale elementary school in Penghu County, as well as the feasible development strategies in the future. In addition, the author summarized and organized these 2 following issues: "Current Implementing Condition of the School Land Reuse Policy for Small-scale Elementary School after Dissolve in Penghu County" and "School Land Reuse Strategy for Small-scale Elementary School after Dissolve in Penghu County". In terms of "Current Implementing Condition of the School Land Reuse Policy for Small-scale Elementary School after Dissolve in Penghu County", the research discovered the government is directing the future reuse plan towards tourism development and multi-purpose usage, and positively trying to resolve the legal restrictions for school reuse. For the solutions to the current problems, strengthened communication with the residents is used to gain a common view on future reuse development. With SWOT analysis, the advantages, disadvantages, opportunities and threats of school reuse are clearly understood. As for the "School Land Reuse Strategy for Small-scale Elementary School after Dissolve in Penghu County", the government is interacting with the community on many occasions to gain their approval on the reuse plan. This would bring community participation, which provides sufficient reasons to relax the legal restrictions for school reuse and encourage the community or public associations to invest. Rental or sale of school land prevents improper reuse management, which causes unused ground again. Community participation plays an important role in the plan by expressing the participation thoughts through neighborhood meeting or community development associations. When there is no reuse of dissolved school land, the current law for donated school land does not state whether the school land is returned to the original donor. The subject gains the approval of most interviewees and this intention urges the government to resolve the current school land reuse problem.

Assimilable organic carbon (AOC) is a suspected contributor to growth of microbes, including pathogens, in plumbing systems. Two phases of research were completed to improve knowledge of AOC and other forms of organic carbon in premise plumbing. In the first phase, the AOC Standard Method 9217B was compared to a new luminescence-based AOC in terms of time, cost, convenience, and sources of error. The luminescence method was generally more accurate, as it better captured the peak growth of the test organisms. It was also less expensive and less time-consuming. A few approaches to improving the accuracy of the method and detect possible errors were also presented. In the second phase of research, the possibility of AOC generation in premise plumbing was reviewed and then tested in experiments. It has been hypothesized that removal of AOC entering distribution systems might be a viable control strategy for opportunistic premise plumbing pathogens (OPPPs), but if AOC was generated in premise plumbing systems this approach would be undermined. Possible sources of AOC creation in premise plumbing, which is herein termed "distribution system derived biodegradable organic carbon (DSD-BDOC)," include: leaching of organic matter from cross linked polyethylene (PEX) pipes, autotrophic oxidation of H2 generated from metal corrosion (e.g. sacrificial magnesium anode rods and iron pipes), rendering of humic substances more biodegradable by sorption to oxides such as Fe(OH)3, and accumulation of AOC on filters and sediments. The potential for various plumbing and pipe materials to generate AOC was compared in controlled simulated water heater experiments. Under the worst-case condition, generation up to 645 µg C/L was observed. IT was not possible to directly confirm the biodegradability of the generated organic carbon, and there were generally no correlations between suspected generation of organic carbon and either heterotrophic plate counts (HPC) or of bacterial 16S rRNA genes. DSD-BDOC was also explored in a simulated distribution system with two disinfectant types (chlorine and chloramine) and three pipe materials (PVC, cement, and iron). TOC increased with water age, probably due to leaching of organics from PVC and possibly the aforementioned DSD-BDOC due to autotrophic reactions of nitrifiers and iron-related bacteria. As before, relationships between the higher levels of organic carbon and either HPC or 16S were not observed. / Master of Science

Currently at the Savannah River Site (SRS), there are fifteen single-shell, 3.6-million liter tanks containing High Level Waste. To close the tanks, the sludge must be removed. Mechanical methods have had limited success. Oxalic acid cleaning is now being considered as a new technology. This research uses sample results and chemical equilibrium software to develop a preferred flowsheet and evaluate the acceptability of the system impacts. Based on modeling and testing, between 246,000 to 511,000 l of 8 wt% oxalic acid were required to dissolve a 9,000 liter Purex sludge heel. For SRS H-Area modified sludge, 322,000 to 511,000 l were required. To restore the pH of the treatment tank slurries, approximately 140,000 to 190,000 l of 50 wt% NaOH or 260,000 to 340,000 l of supernate were required. When developing the flowsheet, there were two primary goals to minimize downstream impacts. The first was to ensure that the Resultant oxalate solids were transferred to DWPF, without being washed. The second was to transfer the remaining soluble sodium oxalates to the evaporator drop tank, so they do not transfer through or precipitate in the evaporator pot. Adiabatic modeling determined the maximum possible temperature to be 73.5°C and the maximum expected temperature to be 64.6°C. At one atmosphere and at 73.5°C, a maximum of 770 l of water vapor was generated, while at 64.6°C a maximum 254 l of carbon dioxide were generated. Although tank wall corrosion was not a concern, because of the large cooling coil surface area, the corrosion induced hydrogen generation rate was calculated to be as high as 10,250 l/hr. Since the minimum tank purge exhaust was assumed to be 5,600 l/hr, the corrosion induced hydrogen generation rate was identified as a potential concern. Excluding corrosion induced hydrogen, trending the behavior of the spiked constituents of concern, and considering conditions necessary for ignition, energetic compounds were shown not to represent an increased risk Based on modeling, about 56,800 l of Resultant oxalates could be added to a washed sludge batch with minimal impact on the number of additional glass canisters produced. For each sludge batch, with 1 to 3 heel dissolutions, about 60,000 kg of sodium oxalate entered the evaporator system, with most collecting in the drop tank, where they will remain until eventual salt heel removal. For each 6,000 kg of sodium oxalate in the drop tank, about 189,000 l of Saltstone feed would eventually be produced. Overall, except for corrosion-induced hydrogen, there were no significant process impacts that would forbid the use of oxalic acid in cleaning High Level Waste tanks. / MATHEMATICAL SCIENCES / M. Tech. (Chemical Engineering)

Currently at the Savannah River Site (SRS), there are fifteen single-shell, 3.6-million liter tanks containing High Level Waste. To close the tanks, the sludge must be removed. Mechanical methods have had limited success. Oxalic acid cleaning is now being considered as a new technology. This research uses sample results and chemical equilibrium software to develop a preferred flowsheet and evaluate the acceptability of the system impacts. Based on modeling and testing, between 246,000 to 511,000 l of 8 wt% oxalic acid were required to dissolve a 9,000 liter Purex sludge heel. For SRS H-Area modified sludge, 322,000 to 511,000 l were required. To restore the pH of the treatment tank slurries, approximately 140,000 to 190,000 l of 50 wt% NaOH or 260,000 to 340,000 l of supernate were required. When developing the flowsheet, there were two primary goals to minimize downstream impacts. The first was to ensure that the Resultant oxalate solids were transferred to DWPF, without being washed. The second was to transfer the remaining soluble sodium oxalates to the evaporator drop tank, so they do not transfer through or precipitate in the evaporator pot. Adiabatic modeling determined the maximum possible temperature to be 73.5°C and the maximum expected temperature to be 64.6°C. At one atmosphere and at 73.5°C, a maximum of 770 l of water vapor was generated, while at 64.6°C a maximum 254 l of carbon dioxide were generated. Although tank wall corrosion was not a concern, because of the large cooling coil surface area, the corrosion induced hydrogen generation rate was calculated to be as high as 10,250 l/hr. Since the minimum tank purge exhaust was assumed to be 5,600 l/hr, the corrosion induced hydrogen generation rate was identified as a potential concern. Excluding corrosion induced hydrogen, trending the behavior of the spiked constituents of concern, and considering conditions necessary for ignition, energetic compounds were shown not to represent an increased risk Based on modeling, about 56,800 l of Resultant oxalates could be added to a washed sludge batch with minimal impact on the number of additional glass canisters produced. For each sludge batch, with 1 to 3 heel dissolutions, about 60,000 kg of sodium oxalate entered the evaporator system, with most collecting in the drop tank, where they will remain until eventual salt heel removal. For each 6,000 kg of sodium oxalate in the drop tank, about 189,000 l of Saltstone feed would eventually be produced. Overall, except for corrosion-induced hydrogen, there were no significant process impacts that would forbid the use of oxalic acid in cleaning High Level Waste tanks. / MATHEMATICAL SCIENCES / M. Tech. (Chemical Engineering)