[pt] Muitos contaminantes orgânicos, incluindo derivados do petróleo, como por exemplo a gasolina, têm baixa solubilidade em água e migram na subsuperfície como uma fase separada da água sendo referidos como NAPLs (non aqueous liquid phases). Em seu processo de migração na subsuperficie os NAPLs deixam para trás segmentos de líquidos disconectados na forma de gânglios ou lentes que constituem a fase residual do contaminante. A presença do contaminante residual constitui-se numa das maiores dificuldades para a implementação de uma técnica adequada de limpeza ou recuperação de locais contaminados, uma vez que tais contaminantes representam uma fonte lenta e continua de contaminação de solos e água subterrânea, especialmente por sua dissolução na água. Nesta tese, estudou-se o efeito do etanol na dissolução de gasolina residual. Tal estudo foi motivado pela necessidade de se obter um melhor entendimento de um cenário de contaminação envolvendo gasolina e etanol uma vez que gasolina com 20 por cento de etanol em sua constituição e etanol puro estão sendo utilizados como combustível, no Brasil, nos últimos 20 anos. O uso de aditivos oxigenados à gasolina, tais como álcoois, objetiva aumentar o desempenho do motor dos automóveis bem como diminuir a emissão de CO2 destes para a atmosfera e este uso vem aumentando em muitos países. Experimentos tipo equilíbrio em lote e experimentos de coluna foram realizados para investigar efeitos do etanol na solubilidade de constituintes da gasolina e no coeficiente de transferência de massa da gasolina para fase aquosa. Colunas de solo arenoso com gasolina em saturação residual foram percoladas por soluções aquosas com diferentes teores de etanol. Os resultados das concentrações efluentes de contaminante ao longo do tempo, obtidas destes ensaios, foram interpretados segundo o modelo de dissolução proposto por Frind et al. (1997), modificado nesta tese para considerar os efeitos de cosolvência do etanol na solubilidade dos constituintes da gasolina. Os resultados experimentais obtidos indicam que um cenário de contaminação envolvendo etanol e gasolina deverá ser bastante diferente daquele de contaminação usual de gasolina.Em um cenário de contaminação envolvendo etanol e gasolina, concentrações mais altas de contaminantes na água serão esperadas bem como diferentes constituintes da gasolina, além do tradicional grupo BTEX (benzeno, tolueno, etilbenzeno e os isômeros xilenos) deverão estar presentes na água em concentrações nocivas ao meio ambiente. / [en] Many organic contaminants, including petroleum products, such as gasoline, have low aqueous solubilities and migrate through the subsurface as a separated phase called NAPLs (non aqueous liquid phases). In its flow path into the porous media the NAPLs let behind disconnected segments of organic liquids entrapped as ganglia or lenses that form the residual phase of the contaminant. The presence of the residual contaminant has been reported as one of the most difficulties in the development of an appropriate cleanup strategy as the residual phase represents a long and continuum source of contamination of soils and groundwater, specially by its dissolution into the water.In this thesis the effect of ethanol on dissolution of residual gasoline was studied, aiming at a better understanding of a scenario of groundwater contamination involving gasoline and ethanol, since 20 percent of ethanol has been added to the Brazilian gasoline in the last 20 years and also ethanol has been used as fuel in Brazil in these years. The use of oxygenated additives into the gasoline, such as alcohols, has the advantage of improving engine performance and reducing the air impact pollution by CO2 and its use has increasing in many countries.Equilibrium batch tests and column experiments were carried out to investigate the effect of ethanol on solubility of gasoline constituents and on the mass transfer coefficient from gasoline to aqueous phase. The results of the column experiments were interpreted with a dissolution numerical model proposed by Frind et al.(1997), modified in this thesis to include the cosolvent effects of the ethanol on the solubility of gasoline constituents.In terms of soil and groundwater contamination related to gasoline spills, chemicals like benzene, toluene, ethylbenzene and xylenes (BTEX group) have acute toxicity or carcinogenicity, are the most water- soluble and mobile gasoline components, receiving the greatest concern. In this work, an enormous enhancement of gasoline constituents solubility due to ethanol was observed, and it was also noticed that the mass transfer coefficient diminished due to ethanol. The highest increase in solubility were for the less water soluble components. Therefore, gasoline components, other than BTEX, are expected in significant concentrations, in a scenario of contamination involving ethanol and therefore more concern about this potential threat should be addressed.

Bwaise III in Kampala, Uganda is a densely populated informal settlement with a shallow groundwater table and inadequate basic services. High risk of groundwater contamination will bring health problem to the local residents. In this study, a large dimension (300 m in length) 2D model was developed to depict the hydrogeological condition and to examine the response to different rainfall infiltration rate on the groundwater table. The boundary condition of the drainage system plays an important role in modeling the groundwater flow. The simulation results show that water in the drain will flow into the aquifer when the drain is full, otherwise the drain will act as a sink for ground water. Advective transport of phosphorus results in no pollutants reaching or percolating into the drain. The integration of phosphorous concentra-tion flowing out of Domain 3 (pollutant inlet) corresponds to the infiltration rate and the plume moves faster during the wet season which brings in more phosphorous compared with the dry season. With sorption, all the phosphorus was adsorbed within the top soil. A simplified 3D model was set up to illustrate the flow field. Additional simulation can be undertaken within this 3D frame for more realistic calculation and consistent prediction.

No description available.

The unsaturated zone could provide an effective barrier against pathogenic microbes entering the groundwater. Knowledge relating to microbial fate in this zone is therefore important for increased understanding of groundwater vulnerability. This thesis examines the published literature that is related to the transport, retention and survival processes that apply to the fecal indicator bacterium Escherichia coli in unsaturated porous media. The main focus concerns the research findings under steady-state flow in homogeneous filter media, and under unfavorable attachment conditions, which are the most common in the natural environment. Experimental results in the literature for the pore-, column- and field-scale are examined and compared to commonly applied theories and modeling approaches. An analysis of the main factors that influence attenuation and biofilm formation is provided. Further, the findings are illustrated in a model of an unplanted, vertical flow constructed wetland. The results indicate that retention at the solid-air-water interface is a major attenuation process. In addition, they suggest that the flow velocity (as dependent on the grain size and the saturation) is a key influencing factor. However, it has not yet been established how the research findings relating to the main processes and influencing factors can be incorporated into predictive models; in the literature, a multitude of models have been proposed and alternative theories could describe the same observation. In this study, the transport and fate of Escherichia coli in different sand filters is, therefore, modeled using various literature models - derived under similar experimental conditions - in order to assess the possibility to compare and generalize the equations, evaluate their implications considering the different saturation settings and filter depths, and to define the spectra of the reduction efficiencies. It is discovered that the bacterial attenuation behaviors vary largely. This calls for clarification regarding the underlying processes. Future research is also recommended to include the ef-fects of structured filter media and sudden changes in the flow rate. / QC 20111208

The American Society of Testing and Materials (ASTM) has established a three tier risk-based corrective action (RBCA) program for cleaning up petroleum release sites, which is supported by the Environmental Protection Agency. RBCA programs make the cleanup of spill sites more efficient by requiring additional site information only when a more accurate risk assessment is needed. For spill sites that do not pass the first tier general assessment, a Tier 2 evaluation involving site specific information and screening level models to assess the potential risk must be conducted. Screening level models generally require site specific input parameters. To increase efficiency it would be helpful to know which parameters have large affects on model output and which parameters do not affect the model output significantly. There have been many studies focused on model sensitivity to input parameters. For an input parameter to vary there must be uncertainty about the value. This research proposes a method of including parameter uncertainty with model sensitivity to quantify the importance of a parameter, where the term importance is a combination of parameter uncertainty and sensitivity. Using the method developed in this thesis, an importance assessment was conducted on an analytical model for vadose zone transport. It was found that for sites posing high risk, with large spill volumes and shallow water table depths, the input parameters of water table depth and spill volume were the most important. The input parameters of precipitation and contaminant biodegradation half-life showed high importance in lower risk situations; when the water table was deep. A comparison of sensitivity analysis to importance showed differences in their results. The sensitivity analysis identified those parameters that the model was sensitive to, while the importance assessment identified the parameters that were sensitive and whose range of uncertainty was large enough to affect model output values. This information could be used for resource allocation decisions when acquiring additional site specific information.

Vattenbehovet stiger i världen till följd av ökande befolkning. Med ökad urbaniseringskapas mer hårdgjorda ytor där föreningar ackumuleras. Dagvattnet transporterar dessa föroreningar som således kan nå grundvattnet. Ett miljömål har antagits i Sverigeför att skydda grundvattentäkter och därmed säkra framtida dricksvattenförsörjning. Rullstensåsar innehåller stora grundvattenmagasin och har hög infiltrationsförmåga för vatten från markytan. Uppsala kommun tar 95 % av sitt dricksvatten från rullstensåsenUppsalaåsen. Ulleråker ligger strax söder om Uppsala stadskärna och i området planerasen ny hållbar stadsdel. Stadsdelen ligger delvis rakt på Uppsalaåsens kärna och det ärviktigt att inget förorenat dagvatten kan infiltrera åsen då det kan påverka dricksvattenförsörjningennegativt. Syftet med detta projekt är att bidra till en djupare förståelse för hur grundvattnet kan påverkas av dagvattenhanteringen vid den planerade nybyggnationen av Ulleråker. Målet med projektet är att utvärdera vad hållbar dagvattenhantering innebär och hur tekniken är planerad att implementeras i Ulleråker. Projektet innefattar även utvärderingav alternativa tekniker som applicerats i andra stadsbyggnadsprojekt med hållbarhetsprofil som skulle kunna tillämpas i Ulleråker. Projektet är till största delen en litteraturstudie där planprogram för Ulleråker studeratsför att identifiera och utvärdera risker som kan uppstå till följd av dagvattenhanteringen,men även för att utvärdera de åtgärder som planeras. En modellering utfördesäven för att studera föroreningsspridning från en bilväg i området. Slutligen studeradesandra stadsbyggnadsprojekt för att se om deras lösningar skulle kunna implementeras i Ulleråker. De främsta riskerna för grundvattenkvaliteten relaterade till dagvattenhantering i Ulleråker har identifierats till släckvatten vid brand, dagvatten- och avloppsledningarsamt utsläpp under byggnationen. Planerade åtgärder är att utifrån sårbarhetsområdensätta restriktioner för markanvändningen och hur byggnationen ska gå till, särskilt vidåskärnan. Dagvattenhantering ska utgå från ett robust dagvattensystem baserat på ettsystemtänk genom att inget dagvatten ska infiltrera marken i sårbara områden. Detta ska säkerställas genom ett tätt vattenledningssystem som avleder dagvattnet till dagvattendammardär det fördröjs och renas. Hantering av släckvatten vid bränder ska ske genom att täta markytor kring byggnader hindrar släckvatten från markinfiltration. Endast vatten får användas som släckvätska. Modelleringen över föroreningsspridning frånen bilväg i Ulleråker visar att föroreningar avsätts på en yta upp till 6 meter från vägbanansmitt. Ett annat stadsbyggnadsprojekt som studerades var Augustenborg i Malmödär dagvattensystemet bygger på öppna lösningar med bland annat kanaler, dammar ochgröna tak. Slutsatserna är att hållbar dagvattenhantering generellt går ut på att fördröja ochrena dagvattnet lokalt. De lösningar som tagits fram för Ulleråkers dagvattenhanteringbygger på täta ledningar och dammar som fördröjer vattnet innan det når ytvattenrecipienten Fyrisån eller kopplas på Uppsala kommuns dagvattenledningar. I Ulleråker blir det viktigt att kontrollprogram finns och efterföljs för att minska risken för förorening av grundvattnet. Föroreningar från Ulleråkersvägen sprids upp till 6 meter ut från vägensmitt och det är således viktigt att täta denna yta så att föroreningarna inte kan infiltreramed dagvattnet ner till Uppsalaåsen. Lösningar från Augustenborg som skulle kunna implementeras i Ulleråker är gröna tak med tjocka jordlager då de renar vatten mer effektivtän tak med tunnare jordlager. / Water demand rises in the world as a result of increasing population. Increased urbanizationcreates more impervious surfaces where pollutants accumulate. The stormwater transports these pollutants, which can thus reach the groundwater. An environmental goal has been adopted in Sweden to protect the groundwater and thus secure future drinking water supply. Eskers contain large groundwater storages and have high infiltration capacity for water fromthe ground surface. Uppsala municipality takes 95 % of its drinking water from the Uppsalaesker. Ulleråker is located just south of Uppsala city centre and in the area a new sustainabledistrict is planned. The district is partly located on the Uppsala esker’s core and it is importantthat no contaminated water is able to infiltrate the esker as it may affect the drinking watersupply negatively. The purpose of this project is to contribute to a deeper understanding of how the groundwatercan be affected by the stormwater management in the planned new construction of Ulleråker.The aim of the project is to evaluate what sustainable stormwater management means andhow the technology is planned to be implemented in Ulleråker. The project also includesevaluation of alternative techniques applied in other urban construction projects with sustainability profile that could be implemented in Ulleråker. The project is mainly a literature study where Ulleråker's plan program has been studied to identify and evaluate risks that may occur as a result of stormwater management, but also to evaluate the planned measures. A modelling was also conducted to study pollutant dispersio nfrom a roadway in the area. Finally, other urban construction projects were studied to see if their solutions could be implemented in Ulleråker. The main risks of groundwater quality related to stormwater management in Ulleråker have been identified as extinguishing water in the event of fire, stormwater and sewage pipelinesand leakage during construction. The planned measures are to impose restrictions on land usebased on vulnerability areas and how the construction is executed, especially at the core of the esker. Stormwater management should be based on a robust water system based on a system thinking so that no water will infiltrate the soil in vulnerable areas. This is to be ensured by a dense water pipeline system that leads the stormwater into surface water dams where it isdelayed and cleaned. Handling of extinguishing water should be done by sealing land surfaces around buildings preventing extinguishing water from soil infiltration. Only water may beused as extinguishing fluid. The modelling of pollution dispersion from a roadway inUlleråker shows that contaminants are deposited on a surface up to 6 meters away from the centre of the roadway. The studied urban building project Augustenborg in Malmö has its stormwater system based on open solutions, including channels, ponds and green roofs. The conclusion is that sustainable stormwater management in general is based on delayingand cleaning stormwater locally. The solutions developed for Ulleråker’s stormwatermanagement are based on dense conduits and ponds that delay the water before reaching thesurface water receptor Fyrisån or are connected to Uppsala municipality's water pipelines. In Ulleråker it becomes important that control programs are in place and followed to reduce therisk of groundwater contamination. Pollution from Ulleråkersvägen is spread up to 6 meters out of the middle of the road and it is therefore important to seal this area so that thecontaminants cannot infiltrate with the stormwater to Uppsalaåsen. Solutions from Augustenborg that could be implemented in Ulleråker are green roofs with thick soil layers asthey clean water more efficiently than roofs with thinner soil layers.

This collection of studies focuses on a PCO system for the oxidation of a model compound, ethanol, using an adsorption-enhanced silica-Ti02 composite (STC) as the photocatalyst; studies are aimed at addressing the optimization of various parameters including light source, humidity, temperature, and possible poisoning events for use as part of a system for gaseous trace-contaminant control system in closed-environment habitats. The first goal focused on distinguishing the effect of photon flux (i.e., photons per unit time reaching a surface) from that ofphoton energy (i.e., wavelength) of a photon source on the PCO of ethanol. Experiments were conducted in a bench-scale annular reactor packed with STC pellets and irradiated with either a UV -A fluorescent black light blue lamp O·max=365 nm) at its maximum light intensity or a UV -C germicidal lamp O.·max=254 nm) at three levels of light intensity. The STC-catalyzed oxidation of ethanol was found to follow zero-order kinetics with respect to C02 production, regardless of the photon source. Increased photon flux led to increased EtOH removal, mineralization, and oxidation rate accompanied by lower intermediate concentration in the effluent. The oxidation rate was higher in the reactor irradiated by UV -C than by UV-A (38.4 vs. 31.9 nM s-1 ) at the same photon flux, with similar trends for mineralization (53.9 vs. 43.4%) and reaction quantum efficiency (i.e., photonic efficiency, 63.3 vs. 50.1 nmol C02 ~mol photons-1 ). UV-C irradiation also led to decreased intermediate concentration in the effluent compared to UV -A irradiation. These results demonstrated that STC-catalyzed oxidation is enhanced by both increased photon flux and photon energy. The effect of temperature and relative humidity on the STC-catalyzed degradation of ethanol was also determined using the UV-A light source at its maximum intensity. Increasing ii temperature from 25°C to 65°C caused a significant decrease in ethanol adsorption (47.1% loss in adsorption capacity); minimal changes in EtOH removal; and ·a dramatic increase in mineralization (37.3 vs. 74.8%), PCO rate (25.8 vs. 53.2 nM s-1 ), and reaction quantum efficiency (42.7 vs. 82.5 nmol C02 J..Lmol phontons-1 ); intermediate acetaldehyde (ACD) evolution in the effluent was also decreased. By elevating the reactor temperature to 45°C, a -32% increase in reaction quantum efficiency was obtained over the use ofUV-C irradiation at room temperature; this also allowed for increased energy usage efficiency by utilizing both the light and heat energy of the UV-A light source. Higher relative humidity (RH) also caused a significant decrease (16.8 vs. 6.0 mg EtOH g STCs-1 ) in ethanol adsorption and dark adsorption 95% breakthrough times (48.5 vs.16.8 hours). Trends developed for ethanol adsorption correlated well with studies using methanol as the target VOC on a molar basis. At higher RH, ethanol removal and ACD evolution were increased while mineralization, PCO rate, and reaction quantum efficiency were decreased. These studies allowed for the development of empirical formulas to approximate EtOH removal, PCO rate, mineralization, and ACD evolution based on the parameters (light intensity, temperature, and RH) assessed. Poisoning events included long-term exposure to low-VOC laboratory air and episodic spikes of either Freon 218 or hexamethylcyclotrisiloxane. To date, all poisoning studies have shown minimal (0-6%) decreases in PCO rates, mineralization, and minimal increases in ACD evolution, with little change in EtOH removal. These results, while studies are still ongoing, show great promise of this technology for use as part of a trace contaminant control system for niche applications such as air processing onboard the ISS or other new spacecrafts.

The overuse and misuse of antibiotics to treat bacterial infections, the release of unmetabolized residuals into the sewer system, and the incomplete removal antibiotic residues by wastewater treatment plants (WWTPs) pose a severe threat to human health. The accumulation of antibiotic residue induces selective pressure on the bacterial population, resulting in the spread of antibiotic-resistant bacteria (ARB) and antibiotic-resistance genes (ARGs) in water. This study investigated the degradation of different types of ARGs in water matrices using a wide variety of treatment technologies. Real wastewater samples were collected from a WWTP in urban Philadelphia and the presence of single and multidrug-resistant bacteria and resistance genes were investigated using molecular-based techniques. Subsequently, an analytical method was developed and validated for the detection and quantification of the ARGs against a range of antibiotics, such as tetracycline (TCN), ciprofloxacin (CIP), and levofloxacin (LVX). Finally, to remove the ARGs from water matrices, different conventional and advanced oxidation processes were applied. At the very onset, conventional treatment processes such as chlorine treatment was used to inactivate the E.coli resistant strains. It was observed that chlorination can potentially deactivate the ARBs by applying a lower dose and contact time. However, the effectiveness of chlorine treatment in removing all types of ARGs from water matrices was limited. For instance, no significant degradation of extracellular ARGs (e-ARGs) was observed in DI water during chlorine treatment. Subsequently, a peracetic acid (PAA) based treatment process was used to degrade the genomic and plasmid-encoded ARGs from the water matrices. Similar to chlorine treatment, no significant changes were observed in the degradation of extracellular ARGs (e-ARGs) in DI and WW. Then, the degradation kinetics of ARGs across different types (gyrAR, tetAR, qnrSR) and forms (chromosomal, plasmids) were evaluated using the Ultraviolet (UV) disinfection process. Compared to chlorination and PAA, UV treatment showed better removal efficiencies for the degradation of different types of e-ARGs in DI water. The degradation profile of e-ARGs showed 1-4 log reductions at a UV fluence of 900 mj/cm2. The i-ARGs showed similar degradation rates as compared to e-ARGs in phosphate buffer saline (PBS) at the same UV dosage. On the other hand, the regrowth potential of ARBs at low UV dosage (60–180 mJ/cm2) showed the evidence of damage repairment after several hours of exposure to light (photoreactivation) and dark conditions, making it susceptible again to the resistance spread. To resolve this issue, process parameters were optimized, and no regrowth of the ARBs were found from the higher fluence from 300 to 600 mJ/ cm2. Later, UV/ H2O2 based AOP was applied to evaluate the degradation and deactivation of the same resistant genes. The addition of H2O2 during the UV treatment produces strongly reactive •OH radicals during the treatment and showed considerable improvements in e-ARGs degradation (1.2-5 logs) compared to UV treatment alone. However, this AOP showed minimal contribution to i-ARG degradation (1-2.4 logs), possibly due to the scavenging of •OH radicals by the cellular components in PBS. In contrast to PBS, the wastewater matrix moderately enhanced the gene degradation during the treatment. In terms of plasmid degradation, the conformational differences of the supercoiled structures showed 1.2-2.8 times slower degradation rates than chromosomal ARGs. In addition, the degradation kinetics of the free residual ARGs (f-ARGs) were assessed during the treatment to reduce the AMR dissemination risk from the treated sample. This study also examined the potential of ozone (O3) based oxidation process to degrade and deactivate the extracellular and intracellular ARGs, and MGE (plasmid, intl-1) from E.coli ARBs. The degradation kinetics of the ARGs across different sizes (118-454 bps) and types were evaluated in different water matrices (DI water, PBS, and WW), and showed a significantly higher removal for chromosomal, and plasmid encoded ARGs than other treatment technologies. For the e-ARGs in DI water, 3.8-5.2 logs removal was observed at ozone dosage of 2.0 × 10-2 M.s. i-ARGs in PBS and wastewater showed nearly similar degradation (3.8-5 logs) during O3, indicating the elimination of i-ARGs was not dependent on the cellular components and effluent organic matter. Moreover, an analysis of environmental DNA (eDNA) from wastewater was conducted to examine the degradation of DNA and ARGs for different storage periods and temperatures (-20°C, 0°C, 4°C, 22±0.87°C). Result indicated that water samples kept at -20°C and 0°C showed the best performance in preventing the DNA concentration and gene degradation over time. Additionally, the effectiveness of different preservatives (Longmire buffers: LB1 and LB2, benzalkonium chloride at 0.1%, 0.01%) were investigated in preserving the DNA integrity and the gene degradation at an ambient temperature. It was found that the Longmire buffer (LB1) exhibited lowest gene degradation during the three-week storage period. In summary, this research provided a comprehensive assessment on the degradation of e-ARGs, i-ARGs, and free ARGs from water using different treatment technologies (i.e., UV, UV/H2O2, O3, PAA, chlorine). Additionally, this study suggested valuable information on optimizing the process parameters of the selected methods and developed a comparative assessment of removing the ARGs from the water matrix (DI/PBS, WW). The estimation of Electrical Energy per Order (EEO, kWh/m3) during UV and ozone treatments provided a comparison of the energy consumption for ARGs degradation in the water. Overall, the findings of this study can be useful for evaluating different types and forms (chromosomal, plasmid) of ARG degradation from water matrices and can help to reduce the risk of AMR dissemination in the environment. / Civil Engineering

Mechanochemically synthesized cobalt oxide-based particles are employed for the catalytic reduction of 4-nitrophenol (4NP), a toxic water contaminant. This reduction produces 4‑aminophenol (4AP), a less toxic, pharmaceutical precursor for drugs such as paracetamol. The indicated reduction has been completed previously using noble metals and/or catalysts requiring extensive solvent use, and time as part of their preparation. The cost and synthesis of these noble metal catalysts hinders the sustainable broad scale application as an environmental remediation solution. The catalyst synthesis explored in this study utilizes the green chemistry technique of vibratory ball-milling and annealing cobalt oxide-based particles at different temperatures, producing unique agglomerates with differing surface structure and catalytic properties. Additional investigation into the mechanism through temperature, pH, and change in pressure over the reaction is completed. Further analysis shows that these catalysts are efficient for the reduction of 4-amino-3-nitrophenol and 2-amino-5-nitrophenol with unique catalytic rates. Finally, it is found that the application of this reduction in a flow process has potential for use on a broader scale.

No description available.