Development and application of target and non-target techniques for routine analysis, identification of transformation products, and characterization of unknown compounds in water matrices using liquid-chromatography high-resolution mass spectrometry (HRMS) were explored in this dissertation. A novel analytical method based on online-SPE-LC-HRMS was developed for the detection of 18 drugs of abuse (DOAs) in raw sewage water from a college campus. Results showed the presence of 14 DOAs for which amphetamine and 11-nor-9-carcoxy-THC (THC metabolite) were the most prevalent and had the highest potential consumption rates. A second study dedicated to the identification of transformation products (TPs) generated from DOAs was conducted using a combination of HR-MS/MS and metabolic identification and structural elucidation software. Findings confirmed the presence of multiple phase I and II DOA TPs (n=35) in raw sewage influents. Concentrations of all TPs were estimated based on the parent DOAs response factors, and used to calculate the percent mole fraction contributions of each TP to the parent concentrations. High abundance and frequency (compared to the parent drug) was determined for 9 of the TPs coming from drugs like oxycodone, morphine, codeine, methadone, LSD, cocaine, and MDEA. Non-target analysis using HRMS was explored as a tool to characterize, and compare a series of interconnected water matrices along a river system. Several thousands of formulae were generated using automated heuristic rules from the full-scan acquisition at 140,000 resolution. Samples were part of a trajectory covering upstream, effluent, effluent mixing zone, downstream, drinking water intake, and treated drinking water locations. Graphical representations of the data were used to evaluate commonalities among the system. Using this approach, a total of 64 recalcitrant components were identified throughout the samples downstream of the effluent release point. Using a combination of MS/MS and computer-aid software techniques 4 out of the 64 compounds were tentatively confirmed. In addition, comparison of drinking water intake and finalized treated drinking water sites showed the presence of 1,152 chemical entities that were common to both locations; and 1,857 that were unique to the treated drinking water. Therefore, this non-target technique could be used to identify the potential formation of treatment byproducts.

Coastal environments can be highly susceptible to environmental changes caused by anthropogenic pressures and natural events. Both anthropogenic and natural perturbations may directly affect the amount and the quality of water flowing through the ecosystem, both in the surface and subsurface and can subsequently, alter ecological communities and functions. The Florida Everglades and the Sian Ka’an Biosphere Reserve (Mexico) are two large ecosystems with an extensive coastal mangrove ecotone that represent a historically altered and pristine environment, respectively. Rising sea levels, climate change, increased water demand, and salt water intrusion are growing concerns in these regions and underlies the need for a better understanding of the present conditions. The goal of my research was to better understand various ecohydrological, environmental, and hydrogeochemical interactions and relationships in carbonate mangrove wetlands. A combination of aqueous geochemical analyses and visible and near-infrared reflectance data were employed to explore relationships between surface and subsurface water chemistry and spectral biophysical stress in mangroves. Optical satellite imagery and field collected meteorological data were used to estimate surface energy and evapotranspiration and measure variability associated with hurricanes and restoration efforts. Furthermore, major ionic and nutrient concentrations, and stable isotopes of hydrogen and oxygen were used to distinguish water sources and infer coastal groundwater discharge by applying the data to a combined principal component analysis-end member mixing model. Spectral reflectance measured at the field and satellite scales were successfully used to estimate surface and subsurface water chemistry and model chloride concentrations along the southern Everglades. Satellite imagery indicated that mangrove sites that have less tidal flushing and hydrogeomorphic heterogeneity tend to have more variable evapotranspiration and soil heat flux in response to storms and restoration. Lastly, water chemistry and multivariate analyses indicated two distinct fresh groundwater sources that discharge to the phosphorus-limited estuaries and bays of the Sian Ka’an Biopshere Reserve; and that coastal groundwater discharge was an important source for phosphorus. The results of the study give us a better understanding of the ecohydrological and hydrogeological processes in carbonate mangrove environments that can be then be extrapolated to similar coastal ecosystems in the Caribbean.

Lågtempererade värmekällor som ytvatten och borrhålslager kan i samverkan med en värmepump ses som outnyttjade energikällor. En sjö- och borrhålsbaserad anläggning kan ha en hög total effektivitet om både värme och kylbehov finns och en stor fördel är att frikyla kan användas från sjö och borrhål under delar av året. Kungsbrohuset byggdes 2008 - 2010 med målsättningen att bli världens mest energieffektiva kontorsbyggnad. Mer specifikt var målsättningen att köpt energi skulle vara hälften av boverkets regler. Av den totala bruksarean på 27 000 m2 utgörs ca 19 500 m2 av kontorsyta. Anläggningen värms och kyls huvudsakligen av en värmepump med en värmeeffekt på 350 kW. Vintertid används värmepumpen för både värme och kyla då ett stort kylbehov även finns under uppvärmningssäsongen till serverrum mm. När värmepumpen inte räcker till så används fjärrvärme och fjärrkyla/sjökyla för att täcka behovet. Vid byggnationen installerades en ledning mellan kungsbrohuset och centralstationen för att på centralstationen utnyttja frikyla från sjön samtidigt som kungsbrohuset fick möjligheten att utnyttja värmen i köldbärarreturen. Målet med studien var att utvärdera anläggningen med fokus på tre huvudsakliga frågor. Att undersöka om värmepumpen har högsta möjliga temperatur på förångningssidan vintertid var den första. Den andra frågan var om frikyla från sjön utnyttjades optimalt. Den tredje frågan var att jämföra den projekterade energianvändningen med det verkliga utfallet. Studien utfördes genom besiktningar på plats, insamling av energistatistik samt att studera anläggningen genom driftdator, driftkort, flödesscheman etc. Vintertid så har den egna köldbärarreturen använts nästan uteslutande som värmekälla till värmepumpen då dess temperatur är högre än borrhålslagrets. Utnyttjandet av frikyla från sjön har inte fungerat optimalt då fjärrkyla har använts under vintermånaderna trots att sjöns temperatur är låg. Detta kan åtgärdas genom omprogrammering av villkor för aktivering av frikylan. Jämförelsen mellan projekterad köpt fastighetsenergi på 47 kWh/m2, år med det verkliga utfallet visade att användningen är något högre i verkligheten och hamnade på 55 kWh/m2, år efter att processkylan räknats bort då den inte räknas som fastighetsenergi. Anläggningen är totalt sett väldigt effektiv och har en mycket låg användning av köpt energi. Att kylbehov finns även vintertid gör att värmepumpens effektivitet blir maximal då nyttig energi utnyttjas på båda sidorna.

Irgarol 1051 is a common antifoulant toxic to certain marine organisms. Submerged aquatic vegetation (SAV) are exposed to this herbicide when it leaches into the marine environment from painted structures, making SAVs ideal candidates to function as sentinel indicator of contamination. In the initial stage of this study, Coconut Grove and Key Largo Harbor were assessed for environmental exposure to Irgarol. Water, sediment and SAVs were collected, the latter two subject to automated solid phase extraction, and all samples analyzed by GC/MS-SIM for Irgarol and its metabolite, M1. Of the vegetation analyzed, Halodule and Syringodium had the highest capacity to bioaccumulate Irgarol and M1. The root system and leaf contributed negligibly and significantly, respectively, to Irgarol uptake. In the final stage, a transplant between Coconut Grove and Chicken Key showed that the biota Thalassia and Halodule were able to uptake and depurate Irgarol, respectively, over a period of 30 days.

An integrated surface-subsurface hydrological model of Everglades National Park (ENP) was developed using MIKE SHE and MIKE 11 modeling software. The model has a resolution of 400 meters, covers approximately 1050 square miles of ENP, includes 110 miles of drainage canals with a variety of hydraulic structures, and processes hydrological information, such as evapotranspiration, precipitation, groundwater levels, canal discharges and levels, and operational schedules. Calibration was based on time series and probability of exceedance for water levels and discharges in the years 1987 through 1997. Model verification was then completed for the period of 1998 through 2005. Parameter sensitivity in uncertainty analysis showed that the model was most sensitive to the hydraulic conductivity of the regional Surficial Aquifer System, the Manning's roughness coefficient, and the leakage coefficient, which defines the canal-subsurface interaction. The model offers an enhanced predictive capability, compared to other models currently available, to simulate the flow regime in ENP and to forecast the impact of topography, water flows, and modifying operation schedules.

The Oak Ridge National Laboratory, Tennessee, was the site for a number of US Government projects during the 1940s and 1950s including the development of thermonuclear weapons. Chemical processes conducted at the site as part of these projects resulted in contamination of certain building areas at the ORNL. The purpose of this study is to develop a hydraulic-hydrologic computer model via XPSWMM to determine surface water flow rates and water stages within the drainage system during rainfall events and introduce a conservative contaminant into the system to trace peak concentrations of contaminants. The model was calibrated by simulating actual rainfall events over the area of interest. The model results were compared to that of Outfall 211’s monitored data. Trial 1 was most successful, where the cumulative flow rates produced by the model and the monitored data varied only by 0.5 cfs. A sensitivity analysis was completed by varying Manning’s coefficient and infiltration parameters within the area of interest. The sensitivity analysis concluded that the model was responsive to the variations presented; however, only minor differences were determined for the selected range of parameters, indicating robustness of model predictions. A hypothetical conservative contaminant was entered into the system as constant and varied timeseries. The resulting pollutographs produced by XPSWMM aid in the assessment for potential mobilization of contaminants and provide insight to where peak concentrations and loads occur under present conditions. Probability exceedance and probability distribution methods were used to analyze the timeseries of flow and pollutant concentrations collected during this study. Probability exceedance curves determined the percentage of time flooding occurred within the system under various conditions. The flow rates and concentrations produced by the transport analysis were best described by the Generalized Extreme Value, while the loading rates were best described by Log-logistic distribution.

Thesis (M. Sc. (Microbiology)) -- University of limpopo, 2016 / Human activities are known to be the major contributors to contamination of natural water sources. This becomes a serious health risk when the communities rely on the same water sources for their household water needs. The current study investigated the bio-physicochemical quality of surface and ground waters found in a mining area in the Tubatse locality, for their suitability for drinking and other household use. The bacteriological analyses of surface waters showed dominance by genera of the phylum Proteobacteria, followed by Actinobacteria and Firmicutes. The isolates included the genera Aeromonas, Pseudomonas, Cronobacter, Acinetobacter, Enterobacter, Pantoea, Serratia, Bordetella, Kocuria and Streptococcus. This dominance pattern is proportionately similar to the pattern reported on human skin and of gut biota. Enterobacter spp. were the predominant species in the surface waters, followed by Bordetella spp. With regard to ground water, one sample was laden with coliforms whereas the other sample was free of coliforms. Physical quality parameters such as turbidity, colour and (total suspended solids) TSS of the surface and ground water samples were compliant with the set standards for drinking water according to South African water quality guidelines (2005). The concentrations of Zn, [SCN-], Cr, Co, Fe, Ni, Cu, H2O2, Cl2 were determined in the surface and ground waters in dry and wet seasons as well. A non-significant decrease in the levels of Cl2 and [SCN-] and an increase in TDS and Cr were observed in the wet season. All metal and chemical levels in surface and ground water, except Cr, were lower than permitted concentration for drinking water. However the concentrations of Zn, Fe and Co exceeded the normal expected concentrations of < 3.5 μg/L, 0.5 mg/L, < 0.01 mg/L and < 5 μg/L respectively. The sediments and soil samples were digested with aqua regia for Cu, Cr, Fe, Co and Zn analyses. An increase in the levels of Zn, Cr and Co in the wet season was observed. The concentrations of the heavy metals such as Co, Cu and Cr were higher in sediments at the sampling points closer to the mining sites. Cytotoxicity assay was performed with different concentrations, as detected in the water and sediment samples, of Zn, [SCN-], Cr, Co, and Fe on C2C12 (mammalian) cells. An increase in viable cells was observed after treatment with Cr (0.2, 0.45 and 0.9 mg/L), Zn and Fe (1.0 and 2 mg/L), Co (2, 5 and 10 mg/L). Only cells treated with SCN- (3.3, 5.4 and 7.2 mg/L) exhibited a significant decrease in viability. These results demonstrate that the water in the Tubatse municipality is not suitable for drinking and other household purposes without prior treatment which will remove contaminating microorganisms and chemicals and heavy metals.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22058号 / 工博第4639号 / 新制||工||1723(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 米田 稔, 教授 清水 芳久, 教授 高野 裕久 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Microplastics are emerging pollutants in the marine environment, including a range of polymers modified by varying quantities of additives and sorbed pollutants, differing in size, colour, and shape. This study focuses on characterization and quantification through visual characterization of microplastics &gt;300 μm in surface water and at 5-meter depth in the Gulf of Bothnia. A comparison between a reference area and an urban impact area was made to estimate if the water is more polluted near rural or industrial areas. The visual characterization was based on general guidelines provided by GESAMP to minimize the risks of identifying false positives. The concentrations of microplastics were found to be similar in the current study in comparison to other studies in the Baltic Sea. There was insufficient evidence to conclude a difference between the reference area and the urban impact area. A key finding in this study was that fragments, i.e. irregular shaped hard particles having appearance of being broken down from a larger piece of litter were the most abundant type of microplastics particles found. The vast majority of the identified polymers by ATR-FTIR (Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy) consisted of Polyethylene (PE) and Polystyrene (PS)

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22767号 / 工博第4766号 / 新制||工||1745(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 米田 稔, 教授 清水 芳久, 准教授 松井 康人 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM