The wide use and the incomplete metabolism of antibiotics, along with the poor removal efficiency of current treatment systems, results in the introduction of large quantities of antibiotics to the environment through the discharge of treated and untreated wastewater. If not treated or attenuated near the source of discharge, the antibiotics can be distributed widely in the environment. In this research, sulfamethoxazole (SMX), a common sulfonamide antibiotic, was selected as a model compound due to its presence in the environment and its resistance to remediation and natural attenuation. Among the various entry routes, discharges from on-site disposal systems are of particular interest due to the wide use of these systems. The complex nature of subsurface transport downstream of these systems adds difficulties to the removal of SMX from subsurface discharges. For this research, two processes that impact SMX removal, biodegradation and sorption, were examined to determine the primary factors governing the elimination of SMX from septic effluent discharges in the subsurface. To characterize the biodegradation of SMX, batch experiments were conducted with SMX in the presence of septic effluent and soil for both aerobic and anoxic conditions. Results showed that SMX removal was limited in the septic effluent but increased in the presence of soil, demonstrating the important role of the soil in SMX removal in both aerobic and anoxic conditions. Addition of external nutrients (ammonium and sulfate) had small effects on SMX removal, although SMX removal was enhanced under aerobic condition with increased dissolved organic carbon. To overcome the limited sorption of SMX on soil, soil amendments were developed and evaluated using biochar, a green and cost-effective adsorbent. Biochars produced from different types of feedstock were characterized for different pyrolysis temperatures, and their adsorption behaviors were examined and compared with commercial biochar and activated carbon (AC). Adsorption isotherms were developed and adsorption kinetics of soil, biochar and AC were studied. Results showed that adsorption on soil, biochar and AC followed three different kinetics models and their equilibrium isotherms followed the Freunlich model. Higher adsorption rates were achieved with biochars prepared at the higher temperature. A lab-engineered biochar with pine sawdust at 500 °C achieved comparable sorption capacity to AC. SMX transport in subsurface was also explored with saturated soil columns filled with soil that was mixed with biochar at different percentages. Significant SMX removal (including complete elimination at a low flowrate and over 90 % elimination at a high flowrate) for all cases was primarily attributed to biodegradation. These results provide insight into the transport and transformations affecting SMX, and then provide a basis for developing low-cost approaches for the mitigation of SMX.

Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-07-10T19:17:06Z No. of bitstreams: 1 TESELL_5jul.pdf: 8671551 bytes, checksum: c59b1fb1df38a655609d9a3ce6cd7d50 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-07-13T20:27:02Z (GMT) No. of bitstreams: 1 TESELL_5jul.pdf: 8671551 bytes, checksum: c59b1fb1df38a655609d9a3ce6cd7d50 (MD5) / Made available in DSpace on 2018-07-13T20:37:40Z (GMT). No. of bitstreams: 1 TESELL_5jul.pdf: 8671551 bytes, checksum: c59b1fb1df38a655609d9a3ce6cd7d50 (MD5) Previous issue date: 2018-05-16 / The climate changes associated with the increase of greenhouse gases emissions to the atmosphere stand out as one of the greatest current environmental concerns. Extensive research is being conducted in order to reduce the amount of emissions and their impact on climate. Carbon dioxide (CO2) is the main greenhouse gas contributing to this problem. Therefore, it is increasingly important to find solutions to reduce CO2 levels in the atmosphere. Among the feasible techniques to reduce these emissions is the geological storage, which consists of injecting large amounts of this gas into deep underground geological formations. To be effective, CO2 must be trapped in these deep geological formations for at least several centuries. In this context, monitoring of CO2 leakages and seepages to sensitive environments is a key step in the process. Research on monitoring and verification of CO2 leakages in shallow environments are carried out in large areas prepared for controlled injection and leakage of this gas, this techniques for its detection are hard and expensive. In this sense, this study aims to verify the use of microcosms as a biomonitoring tool to control CO2 leakage by conducting controlled injections of CO2 into continuous flow columns under different experimental conditions. For this, physical, chemical and microbiological analyzes were performed in the soil before, during and after percolation of CO2 in the column. These parameters were also analyzed with in situ soil samples. Based on statistical methods at the end of the study, it was observed that the design of the columns was suitable, however, the chosen parameters were insufficient to determine the influence of CO2 on the proposed test conditions. / As mudan?as clim?ticas associadas ? intensifica??o do efeito estufa est?o entre as maiores preocupa??es ambientais atuais. Muita pesquisa tem sido realizada com o intuito de reduzir o impacto dos gases associados ao efeito estufa, dentre eles o di?xido de carbono (CO2). Devido ? grande contribui??o do CO2 para o aquecimento global, ? cada vez mais importante a realiza??o de estudos que visem a diminui??o de seus n?veis na atmosfera. Entre as t?cnicas vi?veis para conter estas emiss?es est? o armazenamento geol?gico de carbono, que consiste em injetar quantidades significativas deste g?s em forma??es geol?gicas. No entanto, para ser efetiva, o CO2 deve ficar retido nestas forma??es geol?gicas profundas, n?o retornando a superf?cie a longo prazo. Assim, o monitoramento de vazamentos de CO2 ? uma etapa fundamental no processo de armazenamento geol?gico. Estes estudos usualmente s?o realizados em ?reas extensas preparadas para testes controlados de inje??o e vazamento de g?s (geralmente trabalhosos e dispendiosos). Este trabalho teve como objetivo verificar a utiliza??o de microcosmos como ferramenta de biomonitoramento no controle de vazamento de CO2, realizando inje??es controladas de CO2 em colunas de fluxo cont?nuo em diferentes condi??es experimentais. Foram realizadas an?lises f?sico qu?micas e microbiol?gicas no solo antes, durante e ap?s a percola??o de CO2 na coluna. Esses par?metros tamb?m foram comparados com amostras do solo in situ. Com base em m?todos estat?sticos no fim do estudo foi observado que o projeto das colunas foi adequado, no entanto, os par?metros escolhidos foram insuficientes para determinar a influ?ncia do CO2 nas condi??es de ensaio proposta.

The relative contributions of bedrock geology, radiometric uranium, till permeability and surficial geology were assessed as predictors of radon in indoor air in the Halifax Regional Municipality (HRM), NS, Canada. Bedrock geology and radiometric uranium were statistically significant predictors (14.4%) of indoor radon, based on available indoor radon data. Permeability was not among the predictors, which was surprising given its importance in past studies. In a follow up field analogue study done in laboratory columns, the permeability and diffusivity, as gas transport mechanisms, were found, as suspected, to be important drivers on the concentrations of radon-222 detected. Given the variable thickness of till in the HRM (< 0.5 m to > 3 m), these experiments highlighted the significance of till thickness, composition, and permeability in predicting the radioactive radon-222 potential.

Major impacts of current and pre-regulatory mining activities on the environment include the generation of acid mine drainage (AMD) and metal(loid)-laden acid sulfate soils. Current remediation techniques are mostly cost prohibitive due to high energy, material, and labor requirement. This study investigated two complementary low-cost methods that harnessed the metal(loid)-removing and acid-neutralizing properties of drinking water treatment residuals (WTRs) and the uptake (phytoremediation) potential of vetiver (Vetiviera zizanioides L.) and pokeweed (Phytolacca americana L.) to attenuate and immobilize metal(loid)s from natural AMD and metal(loid)-contaminated soil. Metals were removed from AMD by using a reverse flow fluidized column filter and hydroponic phytoremediation with vetiver and pokeweed. Metals were immobilized in soil through the amendment with Fe and Ca-WTR complimented by the uptake and translocation of metals by vetiver and pokeweed. Experiments were performed under controlled greenhouse conditions as well as under natural Illinois environment in simulated field conditions. Furthermore, the integrated effects of WTR application and the growth of vetiver on soil erosion were also studied. Physicochemical analysis of AMD and soil samples from the Tab-Simco abandoned mine in the Illinois Coal Basin, U.S.A, showed significant concentrations of major metals and metalloids such as Fe, Al, Mn, Zn, Ni, Cu and As at acidic pH levels. The degree of soil contamination at the site was spatially variable with respect to the location of the main AMD seep. Physical, chemical, agronomic and mineralogical characterization of locally acquired water treatment residuals (WTR) showed that the silty and alkaline (pH ≈ 7.0-9.1) materials also contained significant amounts of plant required micronutrients. The presence of amorphous phases of mostly metal (oxy)hydroxides, alkalinity, and porosity of the WTRs suggested the potential to neutralize acidity and capability to remove metal(loid)s in contaminated soils and AMD. Recorded metal removal (%MR) rate by WTR was rapid in the first 80 min in a batch agitation study, except for Mn. Thus, high metal removal ranging from 99.8% to 84.9% at selectivity sequence of Al>Fe>Cu>Zn and Mn (9.6%) was obtained at equilibrium. The pH of the AMD was also increased from 2.6 to 6.7. Analysis of leachate samples from gravity-drained columns following simulated rain events in a greenhouse study showed reduced concentrations of Al, Fe, Mn, Zn, Cu, As and Pb at sustained neutral pH compared with unamended control columns during the 12 weeks study period. Metal immobilization in soil by the lower amendment rates of WTR was comparable to the higher application rates and also showed lower oxalate extractability of metals. Tissue analysis of pokeweed and vetiver hyperaccumulators showed appreciable uptake of relevant elements although translocation was relatively low in both. The analytical results at the greenhouse scale was reproducible in a simulated field scale study under natural Illinois environmental condition where the best amendment rate including 50 g/kg Fe-WTR and 15 g/kg of Ca-WTR and manure helped to improve metal(loid) retention, soil structure and enhanced vetiver growth which subsequently aided in reducing the rate of erosion to levels comparable to bermudagrass which was used as control. The developed integrated WTR fluidized column and phytoremediation technique with vetiver and pokeweed under hydroponic conditions sequentially removed significant quantities of most heavy metals from AMD. Thus, the overall findings showed that the locally collected WTRs - the otherwise waste materials, showed high metal-removing and acidity-reducing capabilities in AMD and contaminated soil treatment applications. The similarity between the results obtained from the laboratory and simulated field study also showed that laboratory/greenhouse experiments may serve as reliable proxies for field responses in applications such as soil and water conservation in agricultural environments, remediation of abandoned mine lands, as well as wastewater treatment systems.

Between 1970 and 2010 almost one-third of drinking water related waterborne disease outbreaks reported to the US Centers for Disease Control and Prevention were associated with systems dependent on untreated groundwater (i.e., most commonly, household wells). This is unsurprising, given that numerous past efforts to monitor household well water quality have indicated a high prevalence of fecal coliforms and/or E. coli at the point of use. Non-point sources of pollution, including septic tank leakages and poorly constructed drain fields, have been identified as the leading risk factors associated with outbreaks in households dependent on groundwater. Ideally, the integration of emerging source tracking (ST) analyses in well monitoring programs could be used to identify whether the presence of fecal indicator bacteria (FIB) is associated with human or non-human sources in order to inform remediation strategies. However, the application of ST to groundwater has been limited, and the interpretation of data is consequently difficult. This research compares the fate and transport of FIB (E. coli and enterococci) with a chemical (optical brighteners, OB) and a molecular (Bacteroides HF183) ST target in order to evaluate their potential use as indicators of water quality issues in private drinking water systems. Eighteen PVC soil columns were constructed in an outdoor soil column facility to represent small-scale septic drainfield models; they received synchronized doses of primary-treated wastewater twice daily and were monitored bi-weekly over a 7-month period. Columns were subject to variable influent loading rates of wastewater effluent, and differing degrees of soil compromisation (i.e. synthetic solution channels). Results show that while column effluent volume and constituent levels were related to dosage, they were not always related to soil compromisation (ANOVA, p < 0.05). E. coli and enterococci concentrations were associated with effluent volume and OB levels (Spearman's rank, p < 0.05). The presence of Bacteroides HF183 was not strongly associated with the other measured ST target levels (Point-biserial correlation, p < 0.05). Findings from this study suggest surface water ST methodologies may have a role in groundwater quality monitoring efforts. Quantifying the relative recovery of ST targets and FIB from controlled groundwater simulations will assist in the development of strategies to identify non-point sources of human wastewater pollution efficiently and effectively to inform remediation. / Master of Science

Factors influencing natural attenuation of dinitrotoluenes (DNT) in surface soils and the application of monitored natural attenuation (MNA) as a remediation strategy were examined using contaminated soils from Badger Army Ammunition Plant (BAAP). Based on the previous research involving contaminated media obtained from locations at BAAP, and the fact that groundwater at the site is not contaminated, it seemed likely that aerobic biodegradation of DNT is active without intervention, and that natural attenuation may be an effective strategy for managing the contamination that exists at BAAP. Microcosms showed that microbes indigenous to soils are capable of 2,4-DNT mineralization and that DNT will adsorb reversibly and become bioavailable. In column studies 2,4-DNT biodegradation was observed and the nitrite evolved during DNT degradation was presumably removed due to oxidation by nitrite oxidizers. The use of simulated rainwater as influent with no nutrient amendments suggests that nutrients do not limit the biodegradation of low concentrations of DNT in the soil tested. In the chemostat study carried out to study effect lowering of temperature (22㬠15㬠10㬠7.5㠡nd 4㩠on biodegradation of DNT at hydraulic retention time of 2.5 days, no sustained change in the DNT substrate removal was observed with change in temperature, but it had a large effect on the nitrite oxidizers. This suggests that the seasonal fluctuations in temperature will have minimal effect on the DNT removal via biodegradation at temperatures above 0㮠Nitrite oxidizers were active at 22㬠their activity decreased at 15㠡nd ceased at temperatures 10㠡nd lower. Nitrite is generally taken as a line of evidence for biodegradation of DNT. The results from the soil column study and chemostat showed that nitrite measurement should not be always taken as a conclusive indicator of DNT degradation. It should be taken into consideration that absence of nitrite does not necessarily mean absence of DNT biodegradation (probably at high temperatures).

De nombreux produits chimiques se retrouvent dispersés dans l'environnement avec des conséquences parfois néfastes pour les hommes et les écosystèmes. Parmi ces substances figurent les antibiotiques et les stéroïdes hormonaux. Peu de données sont disponibles quant à la présence et le devenir de ces substances dans l'environnement notamment pour le sol, par manque de méthodologies. Nous avons donc mis au point des procédures d'analyse de traces de ces contaminants émergents, dans l'eau et le sol. Nous avons développé des méthodes multi-résidus et inter-familles basées sur des analyses LCMS/ MS. Pour les échantillons aqueux, l'extraction est menée sur phase solide (SPE, OASIS HLB). Les MLQs sont comprises entre 0.09 et 34 ng/L. Pour la matrice solide, la procédure d'extraction est inspirée de la méthode appelée QuEChERS suivie d'une purification SPE. Elle a été validée et des MLQs entre 0.013 et 3 ng/g ont été atteintes. Les tétracyclines et les fluoroquinolones, ont été étudiées séparément car elles ont des propriétés physico-chimiques bien spécifiques les rendant difficiles à extraire correctement du sol avec une méthode inter-familles. La méthode développée sur la matrice sol a permis une étude statistique mettant en exergue l'impact de certains paramètres du sol sur les rendements d'extraction et les effets matrice. Les méthodes ont été appliquées à une étude en colonnes de sol pour obtenir des données sur le transfert, l'accumulation et la dégradation des composés dans le sol / Several chemical products are dispersed in the environment and the consequences can be sometimes harmful for humans and the ecosystems. Among these substances appear the antibiotics and the hormonal steroids. Nowadays, only few data are available on the presence and the fate of these substances in the environment in particular for solid matrices, mainly due to a lack of methodologies. Consequently, methods to analyze traces of « emergent » contaminants in water and soil were carried out. Therefore, multi-residues and inter-families procedures based on LC-MS/MS analysis were established. Concerning the aqueous samples, 23 analytes are extracted with the SPE technique (OASIS HLB). MLQs are between 0.09 and 34 ng/L. For the solid matrix, the extraction procedure of 31 compounds is inspired from the method called QuEChERS and followed by a purification step. This methodology was validated and MLQs between 0.013 and 3 ng/g were obtained. Two antibiotics families, tetracyclines and fluoroquinolones, were studied separately as they have specific physical/chemical properties and are therefore difficult to extract from soil with an inter-families method. Then, the method developed for the soil matrix allowed a statistic study which showed the impact of the soil parameters on the recoveries and matrix effects. Finally, the methodologies were applied to a soil column study which allowed obtaining data on the transfer, accumulation and degradation of the substances in soil

Grape root borer, Vitacea polistiformis (Harris), is an oligophagous pest of grapevines in the eastern USA. Neonates must burrow into the soil to find grape roots. In Virginia, larvae feed on roots for ~2 years, then pupate just beneath the soil surface. Emerging adults leave an empty pupal exuviae at the soil surface around the vine base. There was no relationship between weekly captures in pheromone traps and pupal exuviae counts, indicating that exuviae sampling is most appropriate to assess infestations. Exuviae sampling in Virginia vineyards revealed infestations that ranged from light to very heavy. Eighteen biotic and abiotic variables were measured and used in analyses that assessed their relative contributions to differences in exuviae density. Water holding capacity and clay/sand ratio were most strongly associated with pupal exuviae density; these variables were used to develop a model for predicting the extent of infestation of individual vineyards. The spatial distribution of pupal exuviae was characterized using non-spatial and geospatial techniques. Although the non-spatial method (Taylor's Power Law) indicated that exuviae showed an aggregated distribution in all blocks, spatial methods (variograms, SADIE) revealed aggregated distributions only in blocks with ≥ 0.5 pupal exuviae per vine. Independent pupal exuviae samples for population assessment in vineyards can be achieved using sampling points separated by >8.8 m. Combined results from geospatial analyses and the temporal distribution of pupal exuviae within years enabled the development of a practical and quantitative sampling protocol. Bioassays used to measure the behavioral response of larvae to host stimuli revealed that neonates were attracted to grape root volatiles. In soil column bioassays, larvae moved vertically and horizontally over distances of up to 120 cm and apparently perceived the presence of grape roots from a distance of 5 cm in soil. Results are discussed in relation to their potential implications for monitoring and managing grape root borer. / Ph. D.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / No cultivo de bananeiras faz-se o desbaste de brotaÃÃes e o corte de plantas que jà frutificaram gerando resÃduos lignocelulÃsicos. Os pseudocaules cortados formam a maior porÃÃo desse resÃduo e servem como meio para proliferaÃÃo de pragas na cultura. Na utilizaÃÃo industrial desse resÃduo fibroso gera-se o LÃquido do Pseudocaule da Bananeira (LPCB). Este estudo teve por objetivo avaliar efeitos do LPCB combinado com soluÃÃo nutritiva nos parÃmetros fisiolÃgicos, no crescimento e na nutriÃÃo de mudas da cultivar Prata AnÃ. Mudas micropropagadas foram cultivadas em colunas de PVC de 20 cm de diÃmetro por 65 cm de altura contendo cinco camadas de Argissolo (0-10, 10-20, 20-30, 30-40 e 40-60 cm) e submetidas a cinco dosagens do LPCB (0, 288, 576, 864 e 1152 mL), representados por concentraÃÃes volumÃtricas de Ãgua e o resÃduo (100:0, 75:25, 50:50, 25:75, 0:100, v:v), combinadas com duas concentraÃÃes da soluÃÃo nutritiva de Hoagland (uma forÃa e meia forÃa), utilizando-se cinco repetiÃÃes em cada tratamento. ApÃs 60 dias de cultivo determinou-se a taxa fotossintÃtica, a condutÃncia estomÃtica e o teor de clorofila nas folhas e, na ocasiÃo da colheita, aos 68 dias, obteve-se dados de altura e diÃmetro do pseudocaule, nÃmero de folhas, peso fresco e seco das raÃzes e das partes aÃreas e analisaram-se os teores de N, K e Na das raÃzes e das partes aÃreas das bananeiras. Em camadas de solo avaliaram-se caracterÃsticas microbiolÃgicas e quÃmicas. Os resultados indicaram que LPCB afeta a dinÃmica de nutrientes no solo, favorecendo o acÃmulo de Na e K numa camada mais prÃxima da superfÃcie e reduzindo o pH do solo em camadas sub-superficiais. A aplicaÃÃo do resÃduo incrementou a biomassa microbiana e a respiraÃÃo edÃfica. Maiores doses do resÃduo resultaram no menor crescimento e acÃmulo de biomassa da parte aÃrea. A aplicaÃÃo de doses crescentes do resÃduo resultou no incremento da taxa fotossintÃtica e na reduÃÃo da condutÃncia estomÃtica, transpiraÃÃo e teor de clorofila das folhas das bananeiras. / The cultivation of banana trees generate lignoselulosic residue by cutting shoots and the plants after bunch collection. The pseudo-stem represents the largest portion of that residue and serves as a medium for the proliferation of pests in banana field. By industrial processing of that fibrous residue is also generated expressive volume of Netâs speudo-stem (LPCB). This study aimed to evaluate the effects LPCB combined with nutrient solution on physiological parameters, shot growth and nutrition of seedlings of the cultivar âPrata AnÃâ. Plantlets were grown on PVC columns of 20 cm diameter by 65 cm high filled with Ultisol from five layers (0-10, 10-20, 20-30, 30-40 and 40-60 cm) and subjected to five dosages of LPCB (0, 288, 576, 864 and 1152 mL, represented by volumetric combinations of water and LPCB (100:0, 75:25, 50:50, 25:75, 0:100, v:v), combined with two concentrations of Hoagland nutrient solution (one strength and half strength), using five replicates for each treatment. After 60 days of plant cultivation the stomata conductance, photosynthetic and chlorophyll contents in leaves were determined and, at the time of harvest, 68 days, were measured plant height and pseudo-stem diameter, counted leaves, determined fresh and dry weight of roots and aerial parts and analyzed N, K and Na contends in roots and aerial parts of banana plants. In layers of soil were evaluated microbiological and chemical characteristics. The results indicated that LPCB affects the dynamics of nutrients in the soil, favoring the accumulation of Na and K in a layer near the surface and reducing the pH in subsurface layers. The LPCB application rates increased microbial biomass and edaphic respiration. A higher dosage of that residue inhibits the plantlet growth and dry weight accumulation. The increasing of LPCB dosages promoted higher photosynthetic rate, but reduces stomata conductance, transpiration and chlorophyll content in leaves of banana plants.

This diploma thesis was focused on the analysis of four compounds from brominated flame retardants group, namely pentabromoethylbenzene, hexabromocyclododecane, hexabromobenzene and tetrabromobisphenol A. Matrices were represented by four soil samples and four seat of fire samples. In addition, bisphenol A was also determined. First of all, process of extraction of analytes from matrices was optimized. Three different extraction techniques were tested (pressurized solvent extraction, microwave-assisted extraction and ultrasound-assisted extraction). Next step was to verify stability of target compounds in strongly acidic conditions and to optimize clean-up of extract by column chromatography. Gas chromatography with electron capture detection (GC-ECD) was chosen as an appropriate analytical method for the determination of brominated flame retardants. Bisphenol A was determined by gas chromatography with mass spectrometric detection (GC-MS). The derivatization of phenolic analytes before their final analytical determination was also essential.