Desenvolvimento e validação de métodos para a determinação de agrotóxicos em água e solo das áreas de recarga de Aquífero Guarani, na região das nascentes do Rio Araguaia, MT/GO.

Abstract: The area near the Araguaia River, between Goiás and Mato Grosso States, is the location of a portion of the recharging of the Guarani Aquifer, which is one of the world¿s largest aquifer systems and an important source of drinking water. This reservoir could be threatened by the widespread use of pesticides in maize and soybean cultivation in this area. Thus, this work developed analytical methods for the determination of imazethapyr, nicosulfuron, imazaquin, carbofuran, atrazine, linuron, clorimuronethyl and diflubenzuron, pesticides used in maize and soybean cultivation. Pesticide separation, identification and quantification were performed using High-Performance Liquid Chromatography with Diode Array Detection (HPLC-DAD) and Liquid Chromatography-Electrospray Ionization Tandem Mass Spectrometry (LC-ESI-MS/MS). Solid Phase Extraction (SPE) with C18 sorbents was optimized for sample extraction from water. Soil samples were extracted by mechanical shaking, sonication or microwave-assisted extraction with industrial and home microwave ovens. Methods were validated resulting in limits of quantification (LOQ) for the pesticides in water in the range of 0.015-0.1 ng mL, using SPE-HPLC-DAD, and 0.01 ng mL using LC-ESI-MS/MS. LOQ of 1 ng mL for all pesticides in soil were achieved using the home microwave oven and LC-ESI-MS/MS. Recoveries for pesticides with all methods were in the range 70-120 %. Relative standard deviations for repeatability and intermediate precision were less than 15 %. SPEHPLC- DAD and LC-ESI-MS/MS were employed for the analysis of samples of water from the recharge area and most of the pesticides were detected at concentrations below the minimum residue limit (MRL) of 0.1 ng mL established by the European Community. The home microwave oven and LC-ESI-MS/MS were used for the analysis of soil samples from two other regions of Brazil and the pesticides were not detected in these samples. Adsorption and desorption parameters were determined for imazethapyr, imazaquin, nicosulfuron and chlorimuron-ethyl, indicating that these pesticides have little affinity for the soil of the region of the Guarani Aquifer recharge, and show significant leaching potential, according to the ground water ubiquity score (GUS index) for these pesticides.

Estudo paramétrico da recuperação de petróleo pesado por aquecimento eletromagnético resistivo

Electrical resistive heating (ERH) is a thermal method used to improve oil recovery. It can increase oil rate and oil recovery due to temperature increase caused by electrical current passage through oil zone. ERH has some advantage compared with well-known thermal methods such as continuous steam flood, presenting low-water production. This method can be applied to reservoirs with different characteristics and initial reservoir conditions. Commercial software was used to test several cases using a semi-synthetic homogeneous reservoir with some characteristics as found in northeast Brazilian basins. It was realized a sensitivity analysis of some reservoir parameters, such as: oil zone, aquifer presence, gas cap presence and oil saturation on oil recovery and energy consumption. Then it was tested several cases studying the electrical variables considered more important in the process, such as: voltage, electrical configurations and electrodes positions. Energy optimization by electrodes voltage levels changes and electrical settings modify the intensity and the electrical current distribution in oil zone and, consequently, their influences in reservoir temperature reached at some regions. Results show which reservoir parameters were significant in order to improve oil recovery and energy requirement in for each reservoir. Most significant parameters on oil recovery and electrical energy delivered were oil thickness, presence of aquifer, presence of gas cap, voltage, electrical configuration and electrodes positions. Factors such as: connate water, water salinity and relative permeability to water at irreducible oil saturation had low influence on oil recovery but had some influence in energy requirements. It was possible to optimize energy consumption and oil recovery by electrical variables. Energy requirements can decrease by changing electrodes voltages during the process. This application can be extended to heavy oil reservoirs of high depth, such as offshore fields, where nowadays it is not applicable any conventional thermal process such as steam flooding

Análise paramétrica da simulação composicional do processo de Drenagem Gravitacional Assistida por Gás (GAGD)

In Brazil and around the world, oil companies are looking for, and expected development of new technologies and processes that can increase the oil recovery factor in mature reservoirs, in a simple and inexpensive way. So, the latest research has developed a new process called Gas Assisted Gravity Drainage (GAGD) which was classified as a gas injection IOR. The process, which is undergoing pilot testing in the field, is being extensively studied through physical scale models and core-floods laboratory, due to high oil recoveries in relation to other gas injection IOR. This process consists of injecting gas at the top of a reservoir through horizontal or vertical injector wells and displacing the oil, taking advantage of natural gravity segregation of fluids, to a horizontal producer well placed at the bottom of the reservoir. To study this process it was modeled a homogeneous reservoir and a model of multi-component fluid with characteristics similar to light oil Brazilian fields through a compositional simulator, to optimize the operational parameters. The model of the process was simulated in GEM (CMG, 2009.10). The operational parameters studied were the gas injection rate, the type of gas injection, the location of the injector and production well. We also studied the presence of water drive in the process. The results showed that the maximum vertical spacing between the two wells, caused the maximum recovery of oil in GAGD. Also, it was found that the largest flow injection, it obtained the largest recovery factors. This parameter controls the speed of the front of the gas injected and determined if the gravitational force dominates or not the process in the recovery of oil. Natural gas had better performance than CO2 and that the presence of aquifer in the reservoir was less influential in the process. In economic analysis found that by injecting natural gas is obtained more economically beneficial than CO2

Enquadramento dos corpos hídricos subterrâneos do Distrito Federal : parâmetros hidrogeoquímicos e ambientais

Dissertação (mestrado)—Universidade de Brasília, Instituto de Geociências, 2016.

A Hydrogeologic Evaluation of the Waterloo Area in the Upper Jefferson River Valley, Montana

The Upper Jefferson River is one of the most dewatered rivers in Montana. The river exists in an intermontane basin filled with sediment transported from the Highland Mountains to the west, the Tobacco Root Mountains to the east, and the Jefferson River from the south. The Upper Jefferson River Valley is highly dependent on the Jefferson River as the main industry in the valley is agriculture. A majority of the valley is irrigated and used to grow crops, and a good portion is also used for cattle grazing. The residents of the Upper Jefferson River Valley use the aquifer as the main source of potable water. The Jefferson River is also widely used for recreation. This study took place in the Waterloo area of the Upper Jefferson River Valley, approximately 20 miles south of Whitehall, Montana. The Waterloo area provides significant groundwater base flow to the Jefferson River, which is particularly important during the late irrigation season when the river is severely dewatered, and elevated surface-water temperatures occur, creating irrigation water shortages and poor trout habitat. This area contains two springfed streams, Willow Springs and Parson’s Slough, which discharge to the Jefferson River providing cool water in the late season as well as providing the most important trout spawning habitat in the valley. The area is bordered on both the east and west by irrigation ditches, and about 60% of the study area is irrigated. Tile drains were installed in the study area in close proximity to Parsons Slough causing some concern by neighboring residents. This study evaluated relationships between surface water, groundwater, and irrigation practices so that water managers and others can make informed management decisions about the Upper Jefferson River. Data was collected via a network of groundwater wells and surface-water sites. Additionally, water-quality samples were taken and an aquifer test was conducted to determine aquifer properties. The field data were analyzed and a groundwater budget was created in order to evaluate the aquifer. Results of the groundwater budget show that seepage from the irrigation canals and irrigation recharge have the biggest influence on recharge of the aquifer. There is significant groundwater outflow from the aquifer in the spring-fed streams as well as discharge to the Jefferson River. In comparing previous study results to this study’s results, there is no evidence of the water table decreasing due to irrigation practice changes or tile drain installation. However, given the amount of recharge irrigation practices contribute to the aquifer, if significant changes were made, they may affect groundwater elevations. Also lining the irrigation ditches would have a significant impact on the aquifer, as the amount of seepage would be greatly reduced.

Effect of gamma-irradiation on total organic carbon and trihalomethane formation potential

This research was conducted to study the use of radiation in water treatment as an alternative to chlorination which has caused health concerns due to the formation of harmful disinfection by-products. Groundwater solutions from the Biscayne aquifer were radiated with Cobalt-60 gamma radiation and studied for changes in dissolved organic carbon (DOC), UV absorbance at 254 nm (UV254), fluorescence and trihalomethane formation potential (THMFP). Molecular fractionations were conducted by ultrafiltration. Effect of the combination of radiation/peroxide was studied for DOC and UV254. Radiation showed significant removal in DOC and THMFP. Similar results were seen in the fluorescence and UV absorbance experiments. Radiation/peroxide did not improve the DOC removal. Radiation of the groundwater samples broke the larger molecular weight fractions in to smaller fractions.

Lattice Boltzmann Modeling and Specialized Laboratory Techniques to Determine the Permeability of Megaporous Karst Rock

The Pleistocene carbonate rock Biscayne Aquifer of south Florida contains laterally-extensive bioturbated ooltic zones characterized by interconnected touching-vug megapores that channelize most flow and make the aquifer extremely permeable. Standard petrophysical laboratory techniques may not be capable of accurately measuring such high permeabilities. Instead, innovative procedures that can measure high permeabilities were applied. These fragile rocks cannot easily be cored or cut to shapes convenient for conducting permeability measurements. For the laboratory measurement, a 3D epoxy-resin printed rock core was produced from computed tomography data obtained from an outcrop sample. Permeability measurements were conducted using a viscous fluid to permit easily observable head gradients (~2 cm over 1 m) simultaneously with low Reynolds number flow. For a second permeability measurement, Lattice Boltzmann Method flow simulations were computed on the 3D core renderings. Agreement between the two estimates indicates an accurate permeability was obtained that can be applied to future studies.

Development of Novel Time-Domain Electromagnetic Methods for Offshore Groundwater Studies: A Data Application from Bat Yam, Israel

Recent marine long-offset transient electromagnetic (LOTEM) measurements yielded the offshore delineation of a fresh groundwater body beneath the seafloor in the region of Bat Yam, Israel. The LOTEM application was effective in detecting this freshwater body underneath the Mediterranean Sea and allowed an estimation of its seaward extent. However, the measured data set was insufficient to understand the hydrogeological configuration and mechanism controlling the occurrence of this fresh groundwater discovery. Especially the lateral geometry of the freshwater boundary, important for the hydrogeological modelling, could not be resolved. Without such an understanding, a rational management of this unexploited groundwater reservoir is not possible. Two new high-resolution marine time-domain electromagnetic methods are theoretically developed to derive the hydrogeological structure of the western aquifer boundary. The first is called Circular Electric Dipole (CED). It is the land-based analogous of the Vertical Electric Dipole (VED), which is commonly applied to detect resistive structures in the subsurface. Although the CED shows exceptional detectability characteristics in the step-off signal towards the sub-seafloor freshwater body, an actual application was not carried out in the extent of this study. It was found that the method suffers from an insufficient signal strength to adequately delineate the resistive aquifer under realistic noise conditions. Moreover, modelling studies demonstrated that severe signal distortions are caused by the slightest geometrical inaccuracies. As a result, a successful application of CED in Israel proved to be rather doubtful. A second method called Differential Electric Dipole (DED) is developed as an alternative to the intended CED method. Compared to the conventional marine time-domain electromagnetic system that commonly applies a horizontal electric dipole transmitter, the DED is composed of two horizontal electric dipoles in an in-line configuration that share a common central electrode. Theoretically, DED has similar detectability/resolution characteristics compared to the conventional LOTEM system. However, the superior lateral resolution towards multi-dimensional resistivity structures make an application desirable. Furthermore, the method is less susceptible towards geometrical errors making an application in Israel feasible. In the extent of this thesis, the novel marine DED method is substantiated using several one-dimensional (1D) and multi-dimensional (2D/3D) modelling studies. The main emphasis lies on the application in Israel. Preliminary resistivity models are derived from the previous marine LOTEM measurement and tested for a DED application. The DED method is effective in locating the two-dimensional resistivity structure at the western aquifer boundary. Moreover, a prediction regarding the hydrogeological boundary conditions are feasible, provided a brackish water zone exists at the head of the interface. A seafloor-based DED transmitter/receiver system is designed and built at the Institute of Geophysics and Meteorology at the University of Cologne. The first DED measurements were carried out in Israel in April 2016. The acquired data set is the first of its kind. The measured data is processed and subsequently interpreted using 1D inversion. The intended aim of interpreting both step-on and step-off signals failed, due to the insufficient data quality of the latter. Yet, the 1D inversion models of the DED step-on signals clearly detect the freshwater body for receivers located close to the Israeli coast. Additionally, a lateral resistivity contrast is observable in the 1D inversion models that allow to constrain the seaward extent of this freshwater body. A large-scale 2D modelling study followed the 1D interpretation. In total, 425 600 forward calculations are conducted to find a sub-seafloor resistivity distribution that adequately explains the measured data. The results indicate that the western aquifer boundary is located at 3600 m - 3700 m before the coast. Moreover, a brackish water zone of 3 Omega*m to 5 Omega*m with a lateral extent of less than 300 m is likely located at the head of the freshwater aquifer. Based on these results, it is predicted that the sub-seafloor freshwater body is indeed open to the sea and may be vulnerable to seawater intrusion.

2013 survey of Iowa groundwater and evaluation of public well vulnerability classifications for contaminants of emerging concern (2015)

Studies in Iowa have long documented the vulnerability of wells with less than 50 feet (15 meters) of confining materials above the source aquifer to contamination from nitrate and various pesticides. Recent studies in Wisconsin have documented the occurrence of viruses in untreated groundwater, even in wells considered to have little vulnerability to contamination from near-surface activities. In addition, sensitive methods have become available for analyses of pharmaceuticals and pesticides. This study represents the first comprehensive examination of contaminants of emerging concern in Iowa’s groundwater conducted to date, and one of the first conducted in the United States. Raw groundwater samples were collected from 66 public supply wells during the spring of 2013, when the state was recovering from drought conditions. Samples were analyzed for 206 chemical and biological parameters; including 20 general water-quality parameters and major ions, 19 metals, 5 nutrients, 10 virus groups, 3 species of pathogenic bacteria, 5 microbial indicators, 108 pharmaceuticals, 35 pesticides and pesticide degradates, and tritium. The wells chosen for this study represent a diverse range of ages, depths, confining material thicknesses, pumping rates, and land use settings. The most commonly detected contaminant group was pesticide compounds, which were present in 41% of the samples. As many as 6 pesticide compounds were found together in a sample, most of which were chloroacetanilide degradates. While none of the measured concentrations of pesticide compounds exceeded current benchmark levels, several of these compounds are listed on the U.S. Environmental Protection Agency’s Contaminant Candidate List and could be subject to drinking water standards in the future. Despite heavy use in the past decade, glyphosate was not detected, and its metabolite, aminomethylphosphonic acid, was only detected in two of 60 wells tested (3%) at the detection limit of 0.02 μg/L. Pharmaceutical compounds were detected in 35% of 63 samples. Of the 14 pharmaceuticals detected, six had reported concentrations above the method reporting limit, with the maximum reported concentration of 826 ng/L for acetaminophen. Diphenhydramine was the only pharmaceutical to have two detections above the reporting limit, at 24.5 and 145 ng/L. Eight pharmaceuticals had confirmed detections at concentrations below the method reporting limit. Caffeine was the most frequently detected pharmaceutical compound (25%), followed by the caffeine metabolite, 1,7-dimethylxanthine (16%). Microorganisms were detected in 21% of the wells using quantitative polymerase chain reaction methodologies. The most frequently detected microorganism was the pepper mild mottle virus (PMMV), a plant pathogen found in human waste. PMMV was detected in 17% of samples at concentrations ranging from 0.4 to 6.38 gene copies per liter. GII norovirus, human polyomavirus, bovine polyomavirus, and Campylobacter were also detected, while adenovirus, enterovirus, GI norovirus, swine hepatitis E, Salmonella, and enterohemmorhagic E. coli were not detected. No correlations were found between viruses or pathogenic bacteria and microbial indicators. Wells with less than 50 feet (15 meters) of confining material were shown to have greater incidence of surface-related contaminants; however, significant relationships (p<0.05) between confining layer thickness and contaminants were only found for nitrate and herbicides.

GROUND WATER RECHARGE POTENTIAL OF FRESH WATER WETLANDS ON HILTON HEAD ISLAND. SOUTH CAROLINA

Fresh water wetlands on Hilton Head Island have experienced significant degradation over the past few decades. Fifty per cent of the original fresh water wetlands on the island have been either completely destroyed or significantly altered. This fact, plus the declining water levels experienced periodically, have caused much concern over the importance of the wetlands. A major question concerned the role of the wetlands in the recharge of the local ground water aquifer. The present study was undertaken in order to evaluate the potential of the wetlands for water table recharge.

Coastal lagoons and their watersheds as GWDE: a case study in the southwest coast of Portugal

The study of groundwater dependent ecosystems opened the opportunity to involve specialists of different areas of knowledge in order to obtain answers for complex interrelations between groundwater and the associated ecosystems. The actual study, carried out in two coastal lagoons of the Portuguese SW coast, showed the high dependency of the marine life and vegetation of the lagoons and associated streams discharging in the lagoons on the fresh water supply of these two lagoons and the high contribution they receive from groundwater in the dry period, which corresponds to more than half of each hydrologic year. Every year, the lagoons are artificially opened to the ocean for a few days to a few weeks, which dramatically changes the inside salinity. The sensitivity of these ecological niches is demonstrated by the strong dependence that some species that are more sensitive to high salinity waters show in relation to the entrance of freshwater resultant from the discharge of the phreatic aquifer of Sines sedimentary Basin. The great biodiversity of these lagoons and its precarious balance is only possible to preserve if the aquifer continue to act as a regulatory factor of the lagoon’s salinity. The equilibrium can be changed in the event of overexploitation of the phreatic aquifer, which is not at risk in the near future. In a scenario of climate change the lagoons will benefit from a slow increase in groundwater contribution, due to the rise of sea level, which will be accompanied by a rise in groundwater levels in the aquifer near the sea.

Influence of different land uses on groundwater quality in southern Portugal

In Alentejo region, southern Portugal, differences in groundwater samples from six groundwater bodies covered with different land uses were analysed based on the monitoring plan of the Alqueva multi-purpose project, created in the sequence of the construction of the Alqueva Dam on the Guadiana River, in South Portugal. For most of the groundwater bodies there is a statistical significant difference between magnesium, sulphate, chloride, and phosphate. All of these ions are strongly correlated with land use management. Groundwater, where land is covered by olive groves, has high levels of electric conductivity, calcium, potassium, sulphate, and phosphate. Dry land crops are correlated with calcium, magnesium, chloride and consequently, electric conductivity, phosphates and sulphate. Vineyards are strongly correlated with high sulphate and phosphate levels. This study clearly shows that different land uses within a certain groundwater body influence the water quality in a different way. Therefore, an appropriate soil management should be adjusted to each situation, taking into account the aquifer matrix and the overlying soil.

Modelo hidrogeológico tridimensional do aquífero de Ourém

Enquadra-se o aquífero de Ourém no Sinclinal de Ourém e na Bacia Lusitaniana. Propõe-se um modelo conceptual do aquífero de Ourém que tem em consideração a cota da base e do topo e a espessura da formação geológica que o constitui. Estabelece-se um paralelo entre os Membros da Formação da Figueira da Foz e as características hidrogeológicas do aquífero. Avalia-se o regime de exploração por métodos estatísticos robustos, de onde se concluiu que a captação de água desregulada tem levado a uma descida constante dos níveis piezométricos, atingindo em algumas áreas os 7 cm/mês, independentemente da precipitação anual nos últimos anos. Uma campanha de monitorização definiu o sentido NW-SE como o sentido preferencial de fluxo e a área NW do aquífero de Ourém como a área preferencial de recarga. Analisam-se qualitativamente as condições de fronteira do aquífero. ABSTRACT: A tridimensional conceptual model of the Ourém aquifer is defined, considering its top and bottom. The thickness of Figueira da Foz geological formation was calculated. A parallel between the Members of Figueira da Foz formation and hydrogeological characteristics of the aquifer is established. A robust statistical analysis concludes that the unregulated water abstraction of aquifer has led to a constant decrease of the piezometric levels. ln some areas the decreasing achieves 7 cm/month, independently of the annual rainfall. A piezometric monitoring campaign defines the NW-SE direction inside the preferential flow direction of the aquifer and the area NW of aquifer as the preferred aquifer recharge area. The aquifer boundary conditions are qualitatively evaluated.

Avaliação da vulnerabilidade à contaminação no sistema aquífero Évora-Montemor-Cuba

O principal objectivo desta dissertação é a aplicação de métodos empíricos para proceder à caracterização da vulnerabilidade à contaminação do Sistema Aquífero de Évora Montemor-Cuba, nomeadamente os índices DRASTIC, de Susceptibilidade (IS), GOD e o método EPPNA. A aplicação destes índices permitiu concluir que o Sistema Aquífero de Évora-Montemor-Cuba apresenta a maioria da sua área classificada com um índice de vulnerabilidade à contaminação baixo a moderadamente baixo, enquanto os aquíferos carbonatados apresentam grande parte da sua área classificada com um índice moderadamente alto a alto. O IS revelou-se uma ferramenta extremamente útil para ter uma visão espacial do território do ponto de vista da sua vulnerabilidade, quando associada aos usos do solo. No entanto, a complexidade dos sistemas naturais é sempre maior do que as simplificações necessárias para se poderem utilizar as ferramentas que permitem calcular estes índices, existindo permanentemente imprecisões associadas a estes cálculos. ABSTRACT: The aim of this Project is to apply different methods regarding the assessment of groundwater vulnerability to pollution in the Évora-Montemor-Cuba aquifer, namely the DRASTIC, IS, GOD and EPPNA. The greater area of the Évora-Montemor-Cuba aquifer has a vulnerability to pollution classified as low or moderate to low, while in the limestones aquifers the biggest area is classified as moderate to high or high. The IS index is a very useful tool to provide a spatial intuition of the territory, considering its vulnerability, when associated with the land use. However, the natural systems complexity is bigger than the necessary simplifications introduced in order to use these indexes, nevertheless there are permanent inaccuracies related to these results.

Spatial variability of satured soil hydraulic conductivity in the region of Araguaia River - Brazil.

This study evaluates the spatial variability of saturated hydraulic conductivity in the soil in an area of 51,850 ha at the headwaters of the Araguaia River MT/GO. This area is highly vulnerable because it is a location of recharging through natural water infiltration of the Guarani Aquifer System and an area of intense increases in agriculture since its adoption by growers in the last 30 years. Soil samples were collected at 383 points, geographically located by GPS. The samples were collected from depths of 0 - 20 cm and 60 - 80 cm. Exploratory statistics and box-plot were used in the descriptive analysis and semivariogram were constructed to determine the spatial model. The exploratory analysis showed that the mean hydraulic conductivity in the superficial layer was less than at the level of 60-80 cm; however, the greatest variability evaluated with a coefficient of variation also was from this layer. Data tended towards a normal distribution. These results can be explained by the greater soil compaction in the superficial layer. The semivariogram models, adjusted for the two layers, were exponential and demonstrated moderate and strong dependence, with ranges of 5000 and 3000 utm respectively. It was concluded that soil use is influencing the spatial distribution model of the hydraulic conductivity in the region.