The Waimakariri-Avon River system is an important component of the Christchurch aquifer system and has been identified as one of, if not the, primary groundwater flow path. The Waimakariri-Avon River system is ideally suited to geochemical tracing of surface water- groundwater interaction and while many past studies have been undertaken to characterise this system, in terms of its geochemistry and physical hydrogeological components, there is still a large amount of uncertainty as to how long it takes for groundwater to flow from the Waimakariri River, through the Waimakariri-Avon River groundwater system, to the springs that feed the Avon River. The primary goals of this thesis were to; 1) Constrain the residence time of groundwater connecting the Waimakariri-Avon River groundwater system using stable oxygen and hydrogen isotopes and analysis of anionic concentrations of: chloride, fluoride, nitrate, nitrite, bromide and sulfate, 2) Provide additional evidence of a hydrological connection between the Waimakariri River and the Avon River systems, 3) Present observations of the stable isotopic and anionic response of surface water to rainfall events, 4) Identify stable isotopic and anionic surface water variation along the Waimakariri-Avon River system, and establish the reasons for these. This study presents the use of natural isotopic and anionic tracers to characterise the residence time of the groundwater that flows between the Waimakariri and Avon Rivers, by sampling surface water and meteoric water at sites that are part of the Waimakariri-Avon River system. 375 samples were collected from 10 surface water and 4 rainwater sites distributed across the Waimakariri-Avon River surface water-groundwater flow path between March 5th and August, 2014. Additionally the study provides further stable isotopic evidence of the connection between the Waimakariri and Avon Rivers, as well as presents the variability of surface water chemistry in response to rainfall events. Identification of isotopic and anionic variation along the Waimakariri-Avon River system, by surface water sampling, was also conducted to establish the probable causes of observed variations. This study found that the use of large rainfall events, as natural tracers, was not conclusive in establishing the groundwater residence time of the Waimakariri-Avon River system within the 4.5 month sampling period available. Surface water sampling provided further evidence in support of past studies that have determined an isotopic connection between the Waimakariri River and the Avon River with mean stable isotopic values for the Waimakariri River (-8.85‰ δ18O and-60.65 δD) and Avon River (-8.53‰ δ18O and -58.72 δD) being more similar than those of locally derived meteoric water (-5.48‰ δ18O and -35.13 δD). Observations of surface water chemistry variations thorough time determined and identified clear responses to rainfall events as deviations from baseline values, coinciding with rainfall events. Isotopic variation along the Waimakariri-Avon River system was shown to reflect Waimakariri River derived shallow groundwater with the contributions from rainwater increasing with increased proximity to the Avon River mouth. Anionic profiling of the Waimakariri-Avon River system identified increasing concentrations of chloride, nitrate, sulfate, nitrite and bromide, relative to the Waimakariri River, with increased proximity to the Avon River mouth. Fluoride concentrations were identified in lower concentration, relative to the Waimakariri River, with increased proximity to the Avon River mouth. Fluoride and nitrite concentrations were attributed predominantly, if not entirely, to an atmospheric source as mean concentrations were greater in meteoric waters by a factor of at least 2, compared to surface water samples. Chloride and bromide have been attributed to possible salt water mixing as a result of the interaction of upwelling deeper groundwater with the marine and estuarine sands beneath the upper unconfined aquifer, that act as a confining layer within the Christchurch aquifer system. Nitrate and sulfate concentrations have been attributed to potential fertilizer usage and past land-use impacts. A significant step-change increase in chloride, bromide, nitrate and sulfate concentrations was observed between the surface water sample sites at Avonhead Park and the University of Canterbury. The step-change coincides with the boundary of the upper confining layer within the Christchurch aquifer system, and explains the increases in chloride and bromide concentrations. It also suggests a widely distributed source area as concentrations do not become diluted at the Avon River site, at Hagley Park, , which would be expected from the addition of other tributaries, if they did not have similarly high chloride and bromide concentrations. The area between these two sites has also been identified by Environment Canterbury as potentially impacted by past agricultural land-use practices and may explain the increases in nitrate and sulfate concentrations.

De-icing agents such as road salts is one of the most commonly used winter road management strategies employed in Canada and the United States. However, the use of chloride has caused negative impacts on aquatic habitats and drinking water supplies. The purpose of this study is to develop a methodology using readily available GIS data to identify salt vulnerable areas, through evaluating the impact the application of road salts have on areas of interest and quantifying the vulnerability to the area in order to prioritize implementation of best management practices. The proposed methodology for assigning a vulnerability score to a given watershed has been divided into two receiving receptors; surface water and groundwater recharge. The methodology employs a chloride mass balance approach. The vulnerability assessment was performed on seven sites in four watersheds in the Greater Toronto Area and validated using Hanlon Creek watershed in Guelph, ON.

The Very Low Frequency Electromagnetic (VLF-EM) method, which enables surveying without contact with the ground, is suitable for ground surveys in a wide area and has been used in mapping geology for decades. The technique makes use of signal radiation from military navigation radio transmitters operating in the frequency range of 15-30 kHz. When the electromagnetic wave impinges on the surface it is both reflected back into the air and refracted into the earth. By measuring the shifted reflected magnetic field relative to the primary field, subsurface structures can be constrained. Although the VLF method has been widely used to map geology in the last several decades, few modeling studies have been published. Particularly the effect of topography on VLF measurements is poorly characterized. The objective of my research is to study and simulate the VLF topographic responses, and therefore to distinguish between such responses and actual subsurface resistivity anomalies in VLF-EM data. A few basic models (homogenous half-space, horizontal contact and vertical contact) were first created using the finite-elements modeling software Comsol Multiphysics and verified with theoretical solutions. Subsequently, features such as hills and lakes were incorporated into these basic models and further analyzed. When modeling topographic effects, two relationships between max inphase / max slope and max Quad / max slope versus skin depth / hill width are found, which can be used to predict topographic effects when the slope of a hill and resistivity of the ground are known. Two different sets of field data acquired at Saskatoon’s Diefenbaker Hill and at Cameco’s Cree Extension are compared with the modeling results.

The aim of this study was to examine the metal contributions to and from the lake Råsvalen, in northern Örebro County in Sweden, from incoming and outgoing streams.  The main questions were: what is the metal concentration in the streams? How large is the metal transport from the streams, do the concentrations imply a risk for the biota, and can any source be identified. Water was sampled at six locations at six occasions with two-week intervals. The water samples were analyzed for total metal concentrations. The results were compared to environmental quality standards; EQS and from Swedish environmental protection agency suggested class limits. The concentrations were also compared to deviations from background levels and estimations of risk for biological effects. Metal transport was calculated from the average measured concentrations and water flow data from SMHI. Data from sediment analysis in 1989 was included for information about temporal trends. Zn, Cu, and Pb had concentrations above the limits and therefore they could have an effect on biota in water. Zn had a maximum concentration of 39 µg/l in Storån, which is 12 times higher than limits. Pb was found in a maximum concentration of 4,3 µg/l in Hammarskogsån downstream, which is more than twice as high as EQS. Cu was found in concentration of 6,1 µg/l in Storån downstream. Comparison with estimations of biological effects showed no or little effects except for Pb in Hammarskogsån downstream and Storån showing moderate risk. The stream that contributes most to metal influx is Storån. The stream stands for >80% of the total estimated metal transport. Possible sources could be historical mining, and higher levels upstream may contribute to the metal levels found in Storån.

This study investigates surface water and groundwater interactions in a wetland/peatland region surrounding Fort McMurray, Alberta. This work measured local meteorology, water table variation, and isotope and geochemistry concentrations over a two year period. Results from vertical water budget calculations showed episodic runoff events ranging between 0 and 38 mm/yr. Groundwater evaluations showed limited groundwater gradients with mean hydraulic conductivities of 1.01*10-5 cms-1 (NE7) and 1.78 * 10-5 cms-1 (SM8). Overall, groundwater flux estimates were variable and heterogeneous across the catchments areas. Isotopic composition showed mixing between winter precipitation, groundwater and surface water, with groundwater representing the average input signature. This study showed that runoff events were largely associated with spring freshet and significant summer storm events. / Graduate

Orientador: Sérgio Luís de Carvalho / Banca: Alessandro Minillo / Banca: Cristiano Poleto / Resumo: A contaminação dos ecossistemas aquáticos por compostos farmacológicos intensificou-se nos últimos anos devido ao aumento da produção e ao consumo desenfreado destas substâncias pela população. Estes compostos são encontrados em águas naturais e em efluentes de Estações de Tratamento de Esgoto (ETE), comprovando que sua presença em águas naturais é um indicativo de contaminação por águas residuárias de ETE. A presente pesquisa avaliou a ocorrência de compostos farmacológicos no Córrego da Onça, município de Três Lagoas (MS), bem como as relações específicas entre os pontos de monitoramento do corpo d'água. Assim, foram coletadas mensalmente, em um período de 12 meses amostras de água (1L) em seis pontos distintos representando diferentes seções do córrego. As amostras foram submetidas ao processo de extração em fase sólida e analisadas por cromatografia líquida de alta eficiência. Fármacos como atenolol, diclofenaco, ibuprofeno, naproxeno, paracetamol e piroxicam foram detectados nos pontos de coleta do corpo d'água. Com auxílio de uma ferramenta estatística, os pontos amostrais foram reunidos em duas classes, observando-se maior similaridade entre P1(Lagoa do Meio) e P2 (Lagoa Maior), e entre P4 (Jusante da ETE) e P5 (Novas Nascentes). Os resultados evidenciam a contaminação no córrego por compostos farmacológicos, possivelmente devido aos indícios de ligações clandestinas de esgoto sanitário e/ou não eficiência do sistema utilizado pela ETE do município de Três Lagoas. / Abstract: The contamination of aquatic ecosystems by pharmacological compounds has intensified in recent years due to increased production and consumption of these substances by population. These compounds are found in natural waters and effluents from sewage treatment plants (WTP), confirming that their presence in natural waters is indicative of contamination by wastewater from WTP. This study investigated the occurrence of pharmacological compounds in the Stream of Onça at TrêsLagoas (MS), and the specific relationships between the monitoring points of the waterbody. Water samples were collected monthly, over a period of 12 months (water samples 1L) at six different points representing different sections of the stream. The samples were subjected to the process of solid phase extraction and analyzed by high performance liquid chromatography. Drugs such as atenolol, diclofenac, ibuprofen, naproxen, paracetamol and piroxicam were detected in the sampling points of the waterbody. A statistical tool aided to divide the sites into two classes, with a greater similarity between P1 (Middle Pond) and P2 (Major Pond), and between P4 (Downstream of WTP) and P5 (New springs). The results show that the stream contamination by pharmacological compoundsis an indication of illegal connections of sanitary sewer and/or inefficiency of the system used by WTP of Três Lagoas (MS). / Mestre

Made available in DSpace on 2014-06-11T19:29:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-10-01Bitstream added on 2014-06-13T19:59:00Z : No. of bitstreams: 1 americo_jhp_me_ilha.pdf: 1150853 bytes, checksum: 22eb0045ed6531c06a06108c015b424b (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A contaminação dos ecossistemas aquáticos por compostos farmacológicos intensificou-se nos últimos anos devido ao aumento da produção e ao consumo desenfreado destas substâncias pela população. Estes compostos são encontrados em águas naturais e em efluentes de Estações de Tratamento de Esgoto (ETE), comprovando que sua presença em águas naturais é um indicativo de contaminação por águas residuárias de ETE. A presente pesquisa avaliou a ocorrência de compostos farmacológicos no Córrego da Onça, município de Três Lagoas (MS), bem como as relações específicas entre os pontos de monitoramento do corpo d’água. Assim, foram coletadas mensalmente, em um período de 12 meses amostras de água (1L) em seis pontos distintos representando diferentes seções do córrego. As amostras foram submetidas ao processo de extração em fase sólida e analisadas por cromatografia líquida de alta eficiência. Fármacos como atenolol, diclofenaco, ibuprofeno, naproxeno, paracetamol e piroxicam foram detectados nos pontos de coleta do corpo d’água. Com auxílio de uma ferramenta estatística, os pontos amostrais foram reunidos em duas classes, observando-se maior similaridade entre P1(Lagoa do Meio) e P2 (Lagoa Maior), e entre P4 (Jusante da ETE) e P5 (Novas Nascentes). Os resultados evidenciam a contaminação no córrego por compostos farmacológicos, possivelmente devido aos indícios de ligações clandestinas de esgoto sanitário e/ou não eficiência do sistema utilizado pela ETE do município de Três Lagoas. / The contamination of aquatic ecosystems by pharmacological compounds has intensified in recent years due to increased production and consumption of these substances by population. These compounds are found in natural waters and effluents from sewage treatment plants (WTP), confirming that their presence in natural waters is indicative of contamination by wastewater from WTP. This study investigated the occurrence of pharmacological compounds in the Stream of Onça at TrêsLagoas (MS), and the specific relationships between the monitoring points of the waterbody. Water samples were collected monthly, over a period of 12 months (water samples 1L) at six different points representing different sections of the stream. The samples were subjected to the process of solid phase extraction and analyzed by high performance liquid chromatography. Drugs such as atenolol, diclofenac, ibuprofen, naproxen, paracetamol and piroxicam were detected in the sampling points of the waterbody. A statistical tool aided to divide the sites into two classes, with a greater similarity between P1 (Middle Pond) and P2 (Major Pond), and between P4 (Downstream of WTP) and P5 (New springs). The results show that the stream contamination by pharmacological compoundsis an indication of illegal connections of sanitary sewer and/or inefficiency of the system used by WTP of Três Lagoas (MS).

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Poluentes orgÃnicos emergentes (POEs) ou simplesmente contaminantes emergentes referem-se a qualquer composto quÃmico presente numa variedade de produtos comerciais como medicamentos, produtos de uso veterinÃrio, embalagens de alimentos, produtos de higiene, agrotÃxicos, ou alguns microrganismo. Os POEs podem ser encontrados em matrizes ambientais e biolÃgicas, nÃo sÃo usualmente monitorados ou ainda nÃo possuem legislaÃÃo regulatÃria correspondente, e apresentam risco potencial à saÃde humana e ao meio ambiente. Neste trabalho, foi desenvolvido e validado um mÃtodo para a determinaÃÃo de cafeÃna, ciprofloxacina, 17β-estradiol, 17α-etinilestradiol e dietilestilbestrol, considerados interferentes endÃcrinos. O mÃtodo desenvolvido utilizou extraÃÃo em fase sÃlida (SPE) e cromatografia lÃquida de alta eficiÃncia acoplada a um detector de arranjo de diodos. Foram estabelecidas condiÃÃes cromatogrÃficas com eluiÃÃo por gradiente utilizando acetonitrila e Ãgua ultrapura pH 2,0. O planejamento fatorial realizado por SPE indicou que melhores respostas sÃo alcanÃadas quando utiliza-se o cartucho C18, 500 mL de volume de amostra, pH 3,0 e volume de eluiÃÃo igual a 2,0 mL de metanol 100%. As figuras de mÃrito de validaÃÃo do mÃtodo indicaram seletividade, sensibilidade, linearidade, precisÃo, exatidÃo e robustez satisfatÃrias para a maioria dos compostos estudados. Os limites de detecÃÃo (LD) variaram entre 0,283 e 1,543 μg/L (ppb) e os limites de quantificaÃÃo (LQ) variaram entre 0,944 e 5,142 μg/L (ppb). Foi proposta uma nova estratÃgia de controle de qualidade utilizando padrÃo surrogate, e estabelecido um fator de relaÃÃo (FR) a fim de corrigir as concentraÃÃes dos compostos de interesse em amostras reais. O mÃtodo validado foi aplicado nas anÃlises de Ãgua superficial dos aÃudes que fazem parte do abastecimento de Ãgua da RegiÃo Metropolitana de Fortaleza/CE. Os compostos 17β-estradiol, 17α-etinilestradiol foram detectados numa concentraÃÃo mÃxima de 989 e 980 ng/L, respectivamente. / Emerging organic pollutants (EOP), or Emerging Contaminants, is a term that is used to refer any chemical compound insert in variety of comercial products such as medicines, veterinary products, food packaging, pesticides, or any microorganism. The EOP can be found in environmental and ecological arrays not usually monitore or government unregulated, and poses risks to human health na environment. The methodological approach of this thesis included a developed and validated method to determine caffeine, ciprofloxacin, 17β-estradiol, 17α-ethinylestradiol and diethylstilbestrol, considered endocrine disruptors. The method uses a Solid-Phase Extraction (SPE) and high performance liquid cromatography coupled to a diode array detector. Chromatografic conditions were established by gradiente elution using acetonitrile and ultrapure water (pH = 2). The experimental design performed by SPE showed that better responses are achieved when it is used the cartridge C18, 500 mL sample volume, pH 3,0 and 2,0 mL 100% methanol elution volume. The method validation parameters indicated satisfatory selectivity, sensitivity, linearity, precision, accuracy and robustness. Detection limits (DL) ranged from 0,283 to 1,543 μg/L (ppb) and quantification limits (QL) ranged from 0,944 e 5,142 μg/L (ppb). A new quality control strategy using surrogate standard was proposed, and a relation factors (RF) was established to correct of concentrations of compounds of interest in real samples. The validated method was applied to the analysis of surface waters reservoirs from water supply system in metropolitan region of Fortaleza. The compounds 17β-estradiol, 17α-ethynyl estradiol was detected in a maximum concentration of 989 to 980 ng / L, respectively.

>Magister Scientiae - MSc / The present study investigated the application of a multi-method approach to determine groundwater-surface water (GW-SW) interactions to quantify and characterize the quality of water resources in a fractured rock aquifer system in upper catchment of the Berg River (G10A). Demonstrating methods for improved understanding of groundwater and surface water interactions is important for informing development of strategies that ensure effective utilization and management of water resources. Applying a single method to inform innovative strategies for water resources has proved futile. The current study shows how the use of several methods can provide the basis for devising practical strategies for water resource utilization and management. The three methods were applied as follows: First, the base flow separation was used whereby the Chapman and Lynne & Hollick digital filter algorithms were applied to time-series streamflow data from four stream gauging stations in the catchment. The computation from algorithms on three sites (gauging stations) showed that the mean Base Flow Index (BFI) value ranged between 7%-8% for the 2012-2014 periods. This means that discharges from subsurface water storages dominate stream flows throughout the study period. Secondly, the quality of groundwater and surface water was sampled using standard methods. Piper Diagrams generated on Aquachem™ software and radial charts were used to identify the predominant hydrochemical facies. Results showed that Na-Cl was the predominant GW and SW water-type. This means that both GW and SW are mainly influenced by recharging surface water as well as interaction occurring between the rock matrices and infiltrating water. Multivariate statistical analyses were used to evaluate the factors controlling GW and SW chemistry in the upper Berg River catchment and the results showed that GW and SW are influenced by natural processes. Two main factors (a. & b.) were extracted which explained 71.8% of the variation in both GW and SW physicochemical parameters. These factors include water-rock interactions and the recharge of surface water. Cluster Analysis extracted four major clusters that grouped sites with similar physicochemical characteristics together. Finally, differential stream gauging was applied to a 600m reach above the Berg River Dam. Three 200m sub-reaches were used to compute differences in flows between sub-reaches. Stream flow at each sub-reach was estimated using mass balance equations with electrical conductivity measurements during instant salt tracer injection tests. Results indicated that during both the wet season (high flow) dry season (low flow), the river continuously lost water to the subsurface. This was demonstrated by the 0.91m³/s and 2.24m³/s decrease in stream flow along the 600m reach. Dry season flow decreases were less than wet season flow decreases, indicated by markedly lower flow loss in respect to the wet season. This confirms results of the analysis of base flow separation, which indicated that discharges from subsurface storages dominate stream flows during low flow periods. The differential stream gauging approach did not provide distinct points along the selected stream reach where GW-SW interaction occurred; rather it provided a holistic representation of seasonal flow variations along the selected reach. This study showed that upper Berg River catchment is dependent on discharges from subsurface water storages to maintain dry season flows. Furthermore, this study showed that infiltration of surface water and discharge of subsurface water transfers the respective chemical signature of the contributor, meaning that the transfer of water of suitable quality will reduce contamination in the receiving water body (i.e. surface water). Transfer of water between subsurface and surface water contributed an average of 8% of the gauged flows in the catchment between 2012 and 2014, suggesting that the groundwater recharge process dominates this catchment.

This dissertation focused on developing an integrated surface – subsurface hydrologic simulation numerical model by programming and testing the coupling of the USGS MODFLOW-2005 Groundwater Flow Process (GWF) package (USGS, 2005) with the 2D surface water routing model: FLO-2D (O’Brien et al., 1993). The coupling included the necessary procedures to numerically integrate and verify both models as a single computational software system that will heretofore be referred to as WHIMFLO-2D (Wetlands Hydrology Integrated Model). An improved physical formulation of flow resistance through vegetation in shallow waters based on the concept of drag force was also implemented for the simulations of floodplains, while the use of the classical methods (e.g., Manning, Chezy, Darcy-Weisbach) to calculate flow resistance has been maintained for the canals and deeper waters. A preliminary demonstration exercise WHIMFLO-2D in an existing field site was developed for the Loxahatchee Impoundment Landscape Assessment (LILA), an 80 acre area, located at the Arthur R. Marshall Loxahatchee National Wild Life Refuge in Boynton Beach, Florida. After applying a number of simplifying assumptions, results have illustrated the ability of the model to simulate the hydrology of a wetland. In this illustrative case, a comparison between measured and simulated stages level showed an average error of 0.31% with a maximum error of 2.8%. Comparison of measured and simulated groundwater head levels showed an average error of 0.18% with a maximum of 2.9%.