This dissertation reports on research related to novel water treatment and monitoring techniques for sulfide-laden groundwater supplies. The dissertation is divided into several chapters with four core chapters focused on investigations studying a novel water treatment method or monitoring technique. The first investigation assessed the efficacy of multi-pass spray aeration treatment to remove trihalomethanes (THMs) and to reduce the total THM formation potential (TTHMFP) of an aerated water column post-aeration. A recirculating spray aeration pilot unit was constructed to make this assessment. To assess the effect of multi-pass spray aeration on the TTHMFP, water was recirculated through a fabricated spray nozzle for various lengths of time. Results showed that multi-pass spray aeration can remove chloroform, dichlorobromomethane, dibromochloromethane and bromoform to below detection levels ( < 0.7 ppb) for the waters investigated. Additionally, spray aeration reduced the TTHMFP of chlorinated water. Results suggest multi-pass spray aeration may be a viable treatment option for some bromide container waters. Results also indicate that multi-pass spray aeration removes bromide from the bulk water in the form of organically bound volatile compounds. The second investigation assessed the efficacy of using pre-existing tray aeration infrastructure to comply with disinfection by-product (DBP) regulations. To assess the efficacy of tray aerators to reduce the concentration TTHMs a pilot tray aerator was constructed. Results showed that after five tray passes (each pass consisting of water being passed over five trays) the concentration of TTHMs was below the detection limit ( < 0.7 ppb) for the water investigated. To assess the efficacy of tray aeration at full-scale, a water treatment plant and the distribution system it serves were monitored for eight months. Results showed an approximate 40 ppb reduction in the TTHM concentration at two on-site monitoring locations and the one off-site monitoring location (initial concentrations being approximately 54 ppb, 60 ppb and 73 ppb, respectively). Results suggest that the utility managing the full-scale system could comply with DBP regulations by using the pre-existing tray aeration infrastructure to reduce formed THMs on-site where regulated haloacetic acids are not predominant. The third investigation assessed the efficacy of using biological activated carbon (BAC) to remove disinfection by-product precursor matter to comply with DBP regulations. To research this method, a pilot scale BAC filter was operated for three independent test runs. In addition, two full-scale WTPs using BAC were monitored over time. Results showed an approximate 40 percent removal of dissolved organic carbon (DOC) during the three pilot runs and an approximate 55 percent removal of DOC during full-scale monitoring. Results showed that the reduction in DOC reduced the TTHMFP of BAC treated water. Results suggest that BAC treatment could be a viable treatment option to comply with DBP regulations in the sulfide-laden water studied. The fourth investigation assessed the suitability of oxidation reduction potential (ORP) to monitor the effectiveness of an oxidizing media filter used to remove sulfur from a sulfide-laden groundwater. Results showed that ORP was more useful as a measurement technique as compared to free chlorine residual when assessing filter bed health and regeneration effectiveness. It was determined that when the ORP measurement taken from within the oxidative media layer was below 500 mV, the filter bed was not providing treatment, and manganese could be released. Results showed a significant increase in turbidity ( > 2 NTU) and total manganese ( > 0.05 mg/L) occurred when the ORP within the filter bed dropped below 400 mV. More frequent cycling of the filters was found to be an effective treatment option to maintain ORP values above an identified 400 mV operational threshold.

The disinfection of water for potabilization has proven to be one of the most significant public achievements of the 20th century. Although chemical disinfectants are successfully utilized to inactivate acute pathogenic organisms, they may react with natural organic matter (NOM) to produce potentially-harmful disinfection by-products (DBPs). As a result, the United States Environmental Protection Agency regulates DBPs such as total trihalomethanes (TTHMs) and haloacetic acids (HAAs). The research herein is focused on the formation, removal, and control of TTHMs and HAAs in a small public water system (PWS) in Polk County, Florida (County). Pilot-scale tests were implemented to determine the efficacy of stripping TTHMs using single-pass spray and recirculating tray aeration systems, both operating at flows of 3 gallons per minute. In the spray aerator evaluation, an average TTHM reduction of 29.5% was recorded. With tray aeration, a 46.7% reduction of TTHMs was observed after a single pass through the assembly. The benefits of additional recirculation appeared to decrease significantly after four passes, at a TTHM removal of 85.5%. A raw water blending effort was conducted to model bypass around granular activated carbon (GAC) adsorption vessels. The results demonstrated the feasibility of a 50% blend in full-scale treatment operations. With this blend, chlorine residuals and HAA concentrations were able to be controlled throughout 48 hours of incubation at 30°C. From the data collected, a water quality plan was developed for the County's Waverly PWS. The plan to control the formation of DBPs integrated a recirculating tray aeration process for TTHM stripping complemented with GAC adsorption process for removing DBP precursors. The estimated conceptual operating cost was approximated at $24,000 annually. This cost considered carbon replacement as well as the recirculation pump operation. If the recommended 50% GAC bypass is applied, the conceptual operating cost reduces to approximately $15,250 annually.

The ability to manage leachate during post-closure care (PCC) of a landfill may be increasingly difficult as leachate organic matter (LOM) becomes recalcitrant when a landfill ages, requiring advanced and costly treatment technologies. This research investigated the ability to treat LOM through sunlight driven processes, with a focus on photolysis, to provide insight to landfill owners and operators on the potential of wetlands treatment as a means for reducing long-term risks and costs associated with leachate treatment during PCC. The study was completed in eight batch tests, where leachate was exposed to natural sunlight in central Florida for a period of 90 days. It was hypothesized that through photolytic reactions, in particular photolysis, high molecular weight recalcitrant LOM would be degraded to labile, low molecular weight material. To identify the treatment mechanisms, transformation processes were measured using ultraviolet-visible (UV-Vis) spectroscopy, fluorescence excitation-emission matrix spectroscopy (EEMs), size-exclusion chromatography (SEC), and chemical oxygen demand (COD) from the beginning to the end of the test period. Additionally, the ability for nitrogen species to become bioavailable when exposed to sunlight was evaluated for two of the leachate samples using solid-phase extraction (SPE) to fractionate recalcitrant dissolved organic nitrogen (rDON) and bioavailable dissolved organic nitrogen (bDON). Results suggest that treatment of LOM through sunlight driven processes is possible. Treatment is dependent upon the dilution of leachate and characteristics of the LOM. Dilution must be high enough to allow sunlight to penetrate the depth of the liquid. UV-Vis, EEMs, and SEC show that high molecular weight recalcitrant material is undergoing transformation into lower molecular weight material as a result of photolytic and likely biological reactions promoted by sunlight. The ability for nitrogen to become bioavailable when exposed to sunlight was shown to be dependent upon nitrogen concentrations in the sample.

Landfill leachate is a challenging wastewater to discharge into municipal wastewater treatment plants (WWTPs), the most common approach for leachate management, due to the presence of contaminants that may affect the performance of the treatment plant. Treatment, disposal, and transportation of leachate are expensive and therefore a concern. Currently, sidestream treatment is becoming increasingly common in WWTPs prior to returning the liquid to the plant influent. For this research, a new treatment scheme is introduced combining centrate and leachate to reduce contaminants, recover phosphorous and nitrogen through struvite precipitation, and reduce energy requirements through anaerobic ammonium oxidation (Anammox). By combining the two waste streams, the respective limited nutrients (nitrogen in centrate and nitrogen in leachate) can be removed in a low cost chemical treatment resources can be recovered. Carbon contaminants and remaining nutrients can be removed in subsequent innovative biological treatment units. The objective of this thesis is to conduct a cost analysis and environmental assessment of the proposed novel treatment approach and to compare it to more traditional landfill on-site leachate treatment approaches (e.g., membrane bioreactors (MBR) and sequencing batch reactors (SBR)). The study was completed with the use of spreadsheet-based models. Spreadsheets have been developed to evaluate treatment costs (Capital + O&M) for both the proposed nutrient recovery/biological and traditional on-site leachate treatments. Transportation costs of leachate to the WWTP have been studied and analyzed by the use of a spreadsheet model as a function of distance. Results suggest that treatment using Struvite – Aerobic Granular Sludge – Anammox (SGA) was higher in cost compared to traditional approaches. However, positive outcomes from this process include: lower N_2 O emissions, lower power consumption, struvite fertilizer, and overall recovery of nitrogen and phosphorus with the combination of centrate and leachate.

The applications of green sorption media for stormwater treatment and nutrient removal benefit surface and ground water bodies by reducing non-point source pollution from stormwater runoff. To enhance nitrogen and phosphorus removal, a sequential study was performed to develop an improved green sorption media in this study by including the iron filings into the previous biosorption activated media (BAM). The iron-filings-based green environmental media (IFGEM) are thus composed of sand, tire crumb, clay and ground iron filings in which clay and iron particles are supposed to have salient interactions that cannot be present in BAM. However, the optimal ratio between clay and iron-filings remains unknown. The innovative media recipe was determined from a suite of sequential clay and iron filing contents variations by fixed-bed column testing seven IFGEM recipes with varied clay and iron filing aggregates. The optimal IFGEM recipe (IFGEM-3) was initially determined from the nutrient removal efficiency at three influent conditions obtained from spiked distilled water with three levels of phosphate (0.3, 0.5, 0.7 mg/L) and nitrate (0.9, 1.3, 1.7 mg/L) concentrations designed to mimic in-situ stormwater conditions. The nutrient removal and recovery potential with respect to varying physical and chemical properties of IFGEM were further investigated by response surface method (RSM). Response surface method was later employed to identify the optimal or intelligent IFGEM recipe from simulated nutrient removal results based on the seven IFGEM recipes. The RSM encompassed the modeling of the response surface of three responses (total nitrogen, total phosphorus, and ammonia removal) in relation to clay and iron filing contents. Lastly, to validate the efficacy of the real-world applications, a fixed-bed column study was performed to explore the biological and physicochemical characteristics of IFGEM-3 for nutrient removal in stormwater treatment. The nutrient removals and interactions of microbial population dynamics were analyzed for natural soil, BAM, and two IFGEMs (IFGEM-1 and IFGEM-3) simultaneously for final validation of this bioengineering technology. Results indicate that IFGEM has a great potential to achieve the essential removal of nutrients for stormwater runoff.

The primary objective of this research was to develop, fabricate, evaluate and utilize microelectrodes to metal coupons in artificial water system. In the brass experiment, it presented profiles of direct measurements of free chlorine/monochloramine, oxygen and pH to brass and cement based coupons. In monochloraminated water, brass showed a much faster corrosion process under observation. Profiles showed a less monochloramine consumption with as high as 7% greater oxygen utilization comparing to the brass in free chlorine solution, reflecting oxygen could be a major part of the corrosion initiation process. While cement showed less reactive characteristics to disinfectants and oxygen compared to the brass profiles, however, pH showed a significant rise for cement coupon under monochloramine condition. In galvanic experiment, the developed lead micro-ISE (100 µm tip diameter) showed excellent performance toward soluble lead (Pb2+) with the sensitivity of 22.2 ± 0.5 mV decade-1 and limit of detection (LOD) of 1.22×10-6 M (0.25 mg L-1). The response time was less than 10 seconds with a working pH range of 2.0 – 7.0. Using the lead micro-ISE, lead concentration microprofiles were measured from the bulk to the metal surface over time. Combined with two-dimensional (2D) pH map, this work clearly demonstrated that lead leaching at the metal surface is non-uniform and lower surface pH leads to higher lead leaching from the surface. Once significant pH variation (ΔpH: 6.0) was developed across brass-lead joint coupon, even a small pH change (ΔpH: 0.6) within the Pb/Sn alloy resulted in 4 times different surface lead concentrations (42.93 vs. 11.61 mg L-1) and 5 times different fluxes (18.5×10-6 vs. 3.5×10-6 mg cm-2s-1). Continuous surface lead leaching monitoring and surface characterization found that free chlorine is the primary contributor to lead leaching.

Recycled concrete aggregate (RCA) is a sustainable construction material that is a viable option for use in drainage systems by replacing virgin aggregate. Replacing virgin aggregate with RCA is beneficial from both economic and environmental perspectives. However, the use of RCA as pipe backfill materials may cause a long-term performance issue such as potential clogging due to fines accumulation and calcite precipitation on filter fabric. Previous studies investigated the long-term performance of RCA regarding flow rate. Therefore, this study investigated calcite precipitation potential of RCA. The Accelerated Calcite Precipitation (ACP) procedure was devised and used to estimate "life-time" calcite precipitation of RCA for French Drains. The ACP procedure was studied further and improved to optimize the calcite precipitation procedure. The enhanced method was used to compare the calcite precipitation of limestone and RCA samples - sources with varying chemistry and history. Key findings are (1) the clogging due to calcite precipitation of RCA is not as significant as clogging due to the existing and/or accumulated fines, (2) the calcite precipitation can be increased with a temperature of 75°C and 17-hour heating time, and (3) the potential for calcite precipitation from RCA is not as significant as limestone for Type I underdrain gradation.

The occurrence of elevated temperatures within landfills is a very challenging issue for landfill operators to detect and correct. Little is known regarding the causes of elevated temperatures (ETs) and the number of landfills currently operating under such conditions. Therefore, the goal of this research was to determine which landfills within Florida have been impacted by ETs, and to develop a more complete understanding of the factors that may lead to these landfills becoming elevated temperature landfills (ETLFs). Historical landfill gas wellhead data, waste deposition reports, and landfill site geometry were collected for 27 landfill cells through the FDEP OCULUS database and from landfill operators and owners. These data were evaluated to quantify the statistical characteristics that result in landfills becoming 'elevated' in temperature. Gas data included landfill gas temperatures, methane content, carbon dioxide content, and balance gas readings. Waste deposition information was gathered through solid waste reports for each landfill. Landfill site geometry was found through landfill permits, topographical landfill diagrams, and annual operation reports. Furthermore, landfill maps were created in ArcGIS to observe spatial distribution of ETs in landfills over time. Upon analysis of the landfill gas wellhead data, it was discovered that 74% of studied landfill cells had ET readings; regulatory limits specify a maximum allowable gas temperature of 55 degrees C (131 degrees F). When studying the solid waste reports, it was discovered that 37% of landfill cells contained MSW ash; of these cells, 90% of them are considered ETLFs. Regarding site geometry, it was found that ETLF cells are on-average double the site area and approximately 20 feet deeper than the average non-ETLF cell. Furthermore, results suggest that heat propagation in most landfills is limited; however, heat propagation is possible if gas wells are turned off for an extensive time period.

The adaption of needle-type electrochemical microsensor (or microelectrode) techniques to environmental science and engineering systems has transformed how we understand mass transport in biotic and abiotic processes. Their small tip diameter (5-20μm) makes them a unique experimental tool for direct measurements of analytes with high spatial and temporal resolutions, providing a quantitative analysis of flux, diffusion, and reaction rate at a microscale that cannot be obtained using conventional analytical tools. However, their applications have been primarily limited to understanding mass transport dynamics and kinetics in biofilms. With the advancement of sensor fabrication and utilization techniques, their potential applications can surpass conventional biofilm processes. In this dissertation, microsensors were utilized to elucidate mass transport and chemical reactions in multidisciplinary research areas including biological nutrient uptake, oily wastewater treatment, photocatalytic disinfection, and plant disease management, which have not yet explored using this emerging technology. The main objective of this work was to develop novel microsensors and use them for better understanding various natural and engineered aquatic systems. These include; 1) investigating localized photo-aeration and algal-bacterial symbiotic interaction in an advanced algal-bacterial biofilm process for nutrient removal from wastewater, 2) characterizing oil-in-water emulsions for better understanding bilge water emulsion stability, 3) evaluating sun-light driven photocatalytic reactions using a novel MoS2 nanofilm for water disinfection and microcystins-LR removal, 4) developing a zinc ion-selective microsensor and applying them for monitoring the transport of zinc in citrus trees, and 5) integrating heavy metal detection using anodic stripping voltammetry (ASV) in a microelectrode platform for plant applications. Overall, microsensors capable of measuring pH, oxidation-potential reduction (ORP), dissolved oxygen (DO), ammonia (NH3), hydrogen peroxide (H2O2), and zinc (Zn2+) were developed and applied to the systems described above to significantly contribute to a better understanding of interfacial transport mechanisms in various natural and engineered systems.

Human activities generate surplus nutrients which may lead to algal bloom events in water resources along with serious ecological problems and thus substantial economic losses. Particularly, harmful algal blooms (HABs) represent toxic cyanobacterial blooms which produce cyanotoxins. The primary concerns of HABs are the exposures to a wide variety of cyanotoxins via ingestion of contaminated drinking water, inhalation during recreational activities, and consumption of contaminated fish and shellfish. However, conventional physical and chemical methods are not always possible to efficiently handle these HABs events. It is urgent to develop viable and rapid solutions to control HABs in field and mitigate the effects of HABs in fresh water, particularly in those that serve as sources of drinking water supply. Quaternary ammonium compounds (Quats) represent a wide range of cationic compounds with different formulation that constitutes products for agriculture, domestic and medical and industry. As organic antimicrobial compounds, Quats can be used as alternatives to existing chemical-based technique for HABs control due to its less toxicity and its affinity to variety of surface. In this study, recycled concrete aggregate (RCA) from a regional construction and demolition (C&D) waste recycling facility was used as a sustainable and environmentally friendly substrate and coated with a composite of silica-quaternary ammonium compounds (Fixed-Quat). Then, the algistatic capabilities of imparting antimicrobial properties of Quats to the RCA surface, which involve the covalent attachment of the biocides to the surfaces (sol-gel technique), were evaluated with HABs-causing algal species, Microcystis aeruginosa. Chlorophyll-a was measured to determine the efficiency of HABs mitigation using Fixed-Quat coated RCA in terms of photosynthetic inactivation of the selected algae. OD660 and pH were measured as key parameters to monitor algal cell growth and cement hydration. Notably, a 61% reduction of chlorophyll-a within 6 hours and complete removal of chlorophyll-a within 8 hours were achieved, indicating that Fixed-Quat coated RCA would be efficient in growth inhibition of Microcystis aeruginosa. Overall, with an appropriate design for field application and further evaluations like lifetime of Quat coating and potential recovery of treated algae, the Fixed-Quat antimicrobial coated RCA would be a promising and sustainable alternative to conventional HABs mitigation methods in various aquatic systems.