Assessment of the occurrence and potential effects of pharmaceuticals and personal care products in South Florida waters and sediments

A LLE-GC-MS method was developed to detect PPCPs in surface water samples from Big Cypress National Park, Everglades National Park and Biscayne National Park in South Florida. The most frequently found PPCPs were caffeine, DEET and triclosan with detected maximum concentration of 169 ng/L, 27.9 ng/L and 10.9 ng/L, respectively. The detection frequencies of hormones were less than PPCPs. Detected maximal concentrations of estrone, 17β-estradiol, coprostan-3-ol, coprostane and coprostan-3-one were 5.98 ng/L, 3.34 ng/L, 16.5 ng/L, 13.5 ng/L and 6.79 ng/L, respectively. An ASE-SPE-GC-MS method was developed and applied to the analysis of the sediment and soil area where reclaimed water was used for irrigation. Most analytes were below detection limits, even though some of analytes were detected in the reclaimed water at relatively high concentrations corroborating the fact that PPCPs do not significantly partition to mineral phases. An online SPE-HPLC-APPI-MS/MS method and an online SPE-HPLC-HESI-MS/MS method were developed to analyze reclaimed water and drinking water samples. In the reclaimed water study, reclaimed water samples were collected from the sprinkler for a year-long period at Florida International University Biscayne Bay Campus, where reclaimed water was reused for irrigation. Analysis results showed that several analytes were continuously detected in all reclaimed water samples. Coprostanol, bisphenol A and DEET's maximum concentration exceeded 10 μg/L (ppb). The four most frequently detected compounds were diphenhydramine (100%), DEET (98%), atenolol (98%) and carbamazepine (96%). In the study of drinking water, 54 tap water samples were collected from the Miami-Dade area. The maximum concentrations of salicylic acid, ibuprofen and DEET were 521 ng/L, 301 ng/L and 290 ng/L, respectively. The three most frequently detected compounds were DEET (93%), carbamazepine (43%) and salicylic acid (37%), respectively. Because the source of drinking water in Miami-Dade County is the relatively pristine Biscayne aquifer, these findings suggest the presence of wastewater intrusions into the delivery system or the onset of direct influence of surface waters into the shallow aquifer.

Spatial and Temporal Changes in Groundwater Salinity in South Florida

A combination of statistical and interpolation methods and Geographic Information System (GIS) spatial analysis was used to evaluate the spatial and temporal changes in groundwater Cl− concentrations in Collier and Lee Counties (southwestern Florida), and Miami-Dade and Broward Counties (southeastern Florida), since 1985. In southwestern Florida, the average Cl− concentrations in the shallow wells (0–43 m) in Collier and Lee Counties increased from 132 mg L−1 in 1985 to 230 mg L−1 in 2000. The average Cl− concentrations in the deep wells (>43 m) of southwestern Florida increased from 392 mg L−1 in 1985 to 447 mg L−1 in 2000. Results also indicated a positive correlation between the mean sea level and Cl− concentrations and between the mean sea level and groundwater levels for the shallow wells. Concentrations in the Biscayne Aquifer (southeastern Florida) were significantly higher than those of southwestern Florida. The average Cl− concentrations increased from 159 mg L−1 in 1985 to 470 mg L−1 in 2010 for the shallow wells (<33 m) and from 1360 mg L−1 in 1985 to 2050 mg L−1 in 2010 for the deep wells (>33 m). In the Biscayne Aquifer, wells showed a positive or negative correlation between mean sea level and Cl− concentrations according to their location with respect to the saltwater intrusion line. Wells located inland behind canal control structures and west of the saltwater intrusion line showed negative correlation values, whereas wells located east of the saltwater intrusion line showed positive values. Overall, the results indicated that since 1985, there was a potential decline in the available freshwater resources estimated at about 12–17% of the available drinking-quality groundwater of the southeastern study area located in the Biscayne Aquifer.

Lattice Boltzmann Modeling of Fluid Flow and Solute Transport in Karst Aquifers

A novel modeling approach is applied to karst hydrology. Long-standing problems in karst hydrology and solute transport are addressed using Lattice Boltzmann methods (LBMs). These methods contrast with other modeling approaches that have been applied to karst hydrology. The motivation of this dissertation is to develop new computational models for solving ground water hydraulics and transport problems in karst aquifers, which are widespread around the globe. This research tests the viability of the LBM as a robust alternative numerical technique for solving large-scale hydrological problems. The LB models applied in this research are briefly reviewed and there is a discussion of implementation issues. The dissertation focuses on testing the LB models. The LBM is tested for two different types of inlet boundary conditions for solute transport in finite and effectively semi-infinite domains. The LBM solutions are verified against analytical solutions. Zero-diffusion transport and Taylor dispersion in slits are also simulated and compared against analytical solutions. These results demonstrate the LBM’s flexibility as a solute transport solver. The LBM is applied to simulate solute transport and fluid flow in porous media traversed by larger conduits. A LBM-based macroscopic flow solver (Darcy’s law-based) is linked with an anisotropic dispersion solver. Spatial breakthrough curves in one and two dimensions are fitted against the available analytical solutions. This provides a steady flow model with capabilities routinely found in ground water flow and transport models (e.g., the combination of MODFLOW and MT3D). However the new LBM-based model retains the ability to solve inertial flows that are characteristic of karst aquifer conduits. Transient flows in a confined aquifer are solved using two different LBM approaches. The analogy between Fick’s second law (diffusion equation) and the transient ground water flow equation is used to solve the transient head distribution. An altered-velocity flow solver with source/sink term is applied to simulate a drawdown curve. Hydraulic parameters like transmissivity and storage coefficient are linked with LB parameters. These capabilities complete the LBM’s effective treatment of the types of processes that are simulated by standard ground water models. The LB model is verified against field data for drawdown in a confined aquifer.

Investigation of spatial patterns of ground-water exchange with lakes, using a three-dimensional numerical model

Hydrogeologic variables controlling groundwater exchange with inflow and flow-through lakes were simulated using a three-dimensional numerical model (MODFLOW) to investigate and quantify spatial patterns of lake bed seepage and hydraulic head distributions in the porous medium surrounding the lakes. Also, the total annual inflow and outflow were calculated as a percentage of lake volume for flow-through lake simulations. The general exponential decline of seepage rates with distance offshore was best demonstrated at lower anisotropy ratio (i.e., Kh/Kv = 1, 10), with increasing deviation from the exponential pattern as anisotropy was increased to 100 and 1000. 2-D vertical section models constructed for comparison with 3-D models showed that groundwater heads and seepages were higher in 3-D simulations. Addition of low conductivity lake sediments decreased seepage rates nearshore and increased seepage rates offshore in inflow lakes, and increased the area of groundwater inseepage on the beds of flow-through lakes. Introduction of heterogeneity into the medium decreased the water table and seepage ratesnearshore, and increased seepage rates offshore in inflow lakes. A laterally restricted aquifer located at the downgradient side of the flow-through lake increased the area of outseepage. Recharge rate, lake depth and lake bed slope had relatively little effect on the spatial patterns of seepage rates and groundwater exchange with lakes.

Numerical groundwater flow modeling in the Wakal River basin, India

Increasing dependence on groundwater in the Wakal River basin, India, jeopardizes water supply sustainability. A numerical groundwater model was developed to better understand the aquifer system and to evaluate its potential in terms of quantity and replenishment. Potential artificial recharge areas were delineated using landscape and hydrogeologic parameters, Geographic Information System (GIS), and remote sensing. Groundwater models are powerful tools for recharge estimation when transmissivity is known. Proper recharge must be applied to reproduce field-measured heads. The model showed that groundwater levels could decline significantly if there are two drought years in every four years that result in reduced recharge, and groundwater withdrawal is increased by 15%. The effect of such drought is currently uncertain however, because runoff from the basin is unknown. Remote sensing and GIS revealed areas with slopes less than 5%, forest cover, and Normalized Difference Vegetative Index greater than 0.5 that are suitable recharge sites.

Land Use and Climate Change Impacts on the Hydrology of the Upper Mara River Basin, Kenya: Results of a Modeling Study to Support Better Resource Management

Some of the most valued natural and cultural landscapes on Earth lie in river basins that are poorly gauged and have incomplete historical climate and runoff records. The Mara River Basin of East Africa is such a basin. It hosts the internationally renowned Mara-Serengeti landscape as well as a rich mixture of indigenous cultures. The Mara River is the sole source of surface water to the landscape during the dry season and periods of drought. During recent years, the flow of the Mara River has become increasingly erratic, especially in the upper reaches, and resource managers are hampered by a lack of understanding of the relative influence of different sources of flow alteration. Uncertainties about the impacts of future climate change compound the challenges. We applied the Soil Water Assessment Tool (SWAT) to investigate the response of the headwater hydrology of the Mara River to scenarios of continued land use change and projected climate change. Under the data-scarce conditions of the basin, model performance was improved using satellite-based estimated rainfall data, which may also improve the usefulness of runoff models in other parts of East Africa. The results of the analysis indicate that any further conversion of forests to agriculture and grassland in the basin headwaters is likely to reduce dry season flows and increase peak flows, leading to greater water scarcity at critical times of the year and exacerbating erosion on hillslopes. Most climate change projections for the region call for modest and seasonally variable increases in precipitation (5–10 %) accompanied by increases in temperature (2.5–3.5 °C). Simulated runoff responses to climate change scenarios were non-linear and suggest the basin is highly vulnerable under low (−3 %) and high (+25 %) extremes of projected precipitation changes, but under median projections (+7 %) there is little impact on annual water yields or mean discharge. Modest increases in precipitation are partitioned largely to increased evapotranspiration. Overall, model results support the existing efforts of Mara water resource managers to protect headwater forests and indicate that additional emphasis should be placed on improving land management practices that enhance infiltration and aquifer recharge as part of a wider program of climate change adaptation.

Results of analysis and model simulation of the bed profiles

Bedforms such as dunes and ripples are ubiquitous in rivers and coastal seas, and commonly described as triangular shapes from which height and length are calculated to estimate hydrodynamic and sediment dynamic parameters. Natural bedforms, however, present a far more complicated morphology; the difference between natural bedform shape and the often assumed triangular shape is usually neglected, and how this may affect the flow is unknown. This study investigates the shapes of natural bedforms and how they influence flow and shear stress, based on four datasets extracted from earlier studies on two rivers (the Rio Paraná in Argentina, and the Lower Rhine in The Netherlands). The most commonly occurring morphological elements are a sinusoidal stoss side made of one segment and a lee side made of two segments, a gently sloping upper lee side and a relatively steep (6 to 21°) slip face. A non-hydrostatic numerical model, set up using Delft3D, served to simulate the flow over fixed bedforms with various morphologies derived from the identified morphological elements. Both shear stress and turbulence increase with increasing slip face angle and are only marginally affected by the dimensions and positions of the upper and lower lee side. The average slip face angle determined from the bed profiles is 14°, over which there is no permanent flow separation. Shear stress and turbulence above natural bedforms are higher than above a flat bed but much lower than over the often assumed 30° lee side angle.

Análise computacional de imagens de lâminas delgadas na predição dos parâmetros hidráulicos porosidade e condutividade hidráulica do aquífero Barreiras-RN

The understanding of the occurrence and flow of groundwater in the subsurface is of fundamental importance in the exploitation of water, just like knowledge of all associated hydrogeological context. These factors are primarily controlled by geometry of a certain pore system, given the nature of sedimentary aquifers. Thus, the microstructural characterization, as the interconnectivity of the system, it is essential to know the macro properties porosity and permeability of reservoir rock, in which can be done on a statistical characterization by twodimensional analysis. The latter is being held on a computing platform, using image thin sections of reservoir rock, allowing the prediction of the properties effective porosity and hydraulic conductivity. For Barreiras Aquifer to obtain such parameters derived primarily from the interpretation of tests of aquifers, a practice that usually involves a fairly complex logistics in terms of equipment and personnel required in addition to high cost of operation. Thus, the analysis and digital image processing is presented as an alternative tool for the characterization of hydraulic parameters, showing up as a practical and inexpensive method. This methodology is based on a flowchart work involving sampling, preparation of thin sections and their respective images, segmentation and geometric characterization, three-dimensional reconstruction and flow simulation. In this research, computational image analysis of thin sections of rocks has shown that aquifer storage coefficients ranging from 0,035 to 0,12 with an average of 0,076, while its hydrogeological substrate (associated with the top of the carbonate sequence outcropping not region) presents effective porosities of the order of 2%. For the transport regime, it is evidenced that the methodology presents results below of those found in the bibliographic data relating to hydraulic conductivity, mean values of 1,04 x10-6 m/s, with fluctuations between 2,94 x10-6 m/s and 3,61x10-8 m/s, probably due to the larger scale study and the heterogeneity of the medium studied.

Ocorrência de compostos de interesse emergente no aquífero Dunas-Barreiras e nos esgotos de Natal/RN

The detection of emerging interest microcontaminants in environmental samples of surface water, groundwater, drinking water, wastewater and effluents from water and sewage treatment plants (WTP and STP), in many countries, suggests these pollutants are widespread in the environment, mainly in urban areas. This is a reason for great concern, since many of these compounds are potentially harmful for humans other living beings, and they are not efficiently removed in the majority of WTP and STP, which is exacerbated by precariousness of water supply and sanitation services. In Natal, like other Brazilian cities, the sewage system serves only part of the urban area (about 30%), so that the rest of the wastewater is infiltrated in the sandy soil of the region in cesspool-dry well systems. This has resulted in contamination of groundwater in the area (sand-dune barrier aquifer, which supplies more than 50% of the city population), which has been observed by the increase in nitrate concentration in supply wells. The vulnerability of the sanddune barrier aquifer, combined with reports of the presence of emerging interest microcontaminants in Brazil and worldwide, led to this research, which investigated the occurrence of fifteen microcontaminants in Natal groundwater and sewage. Samples were collected at five wells used for water supply, the raw sewage and the effluents from biological reactors from STP (UASB and activated sludge reactors). Two samples of each sample were taken, with one week apart between the samples. To determine the contaminants, extraction of aquifer water, and raw and treated sewage samples were performed, through the technique of using SPE Strata X cartridge (Phenomenex®) to the aquifer water, and Strata SAX and Strata X (Phenomenex® ) for samples of raw and treated sewage. Subsequently the extracts were analyzed using GC-MS technique. Much of the analyzed microcontaminants were detected in groundwater and sewage. The concentrations in groundwater are generally lower than those found in the sewers. Some of the compounds (estrone, estradiol, bisphenol A, caffeine, diclofenac, naproxen, paracetamol and ibuprofen) are partially removed at STP.

Desempenho de uma lagoa de infiltração na absorção de cheias e na recarga de aquífero

A type of macro drainage solution widely used in urban areas with predomi-nance of closed catchments (basins without outlet) is the implementation of detention and infiltration reservoirs (DIR). This type of solution has the main function of storing surface runoff and to promote soil infiltration and, consequently, aquifer recharge. The practice is to avoid floods in the drainage basin low-lying areas. The catchment waterproofing reduces the distributed groundwater recharge in urban areas, as is the case of Natal city, RN. However, the advantage of DIR is to concentrate the runoff and to promote aquifer recharge to an amount that can surpass the distributed natu-ral recharge. In this paper, we proposed studying a small urban drainage catchment, named Experimental Mirassol Watershed (EMW) in Natal, RN, whose outlet is a DIR. The rainfall-runoff transformation processes, water accumulation in DIR and the pro-cess of infiltration and percolation in the soil profile until the free aquifer were mod-eled and, from rainfall event observations, water levels in DIR and free aquifer water level measurements, and also, parameter values determination, it is was enabled to calibrate and modeling these combined processes. The mathematical modeling was carried out from two numerical models. We used the rainfall-runoff model developed by RIGHETTO (2014), and besides, we developed a one-dimensional model to simu-late the soil infiltration, percolation, redistribution soil water and groundwater in a combined system to the reservoir water balance. Continuous simulation was run over a period of eighteen months in time intervals of one minute. The drainage basin was discretized in blocks units as well as street reaches and the soil profile in vertical cells of 2 cm deep to a total depth of 30 m. The generated hydrographs were transformed into inlet volumes to the DIR and then, it was carried out water balance in these time intervals, considering infiltration and percolation of water in the soil profile. As a re-sult, we get to evaluate the storage water process in DIR as well as the infiltration of water, redistribution into the soil and the groundwater aquifer recharge, in continuous temporal simulation. We found that the DIR has good performance to storage excess water drainage and to contribute to the local aquifer recharge process (Aquifer Dunas / Barreiras).

O sistema aquífero Barreiras na região de Parnamirim, RN: uso das águas e potencialidades

The study area is within the Pirangi River Basin, eastern sector of Rio Grande do Norte state, where is located of the Parnamirim city. It has an area of approximately 370 km². Urbanization has developed much fast without an appropriate infrastructure, mainly by the lack of sewage systems, with risks of contamination of groundwater that may cause serious damage to the health of the population. The Barreiras Aquifer System groundwater in the area represents the main source of water supply for urban and rural populations. The use of groundwater occurs without adequate planning and therefore, important recharge areas are being occupied. This study was conducted to quantify the use and evaluation of the potential of groundwater, in order to increase good water quality supply and lower risks of being affected by polluting activities. With these objectives, the following activities were carried out: 268 points of water have been registered; characterization of the lithological, thickness and hydrogeological structure of the Barreiras aquifer, based on the correlation of well logs; and evaluation of hydrodynamic parameters of the aquifer, from the interpretation of results well pumping tests. It was found that the saturated thickness increases from west to east towards the sea, with values ranging from 15,47-56,5 m with an average of 32,45 m. The hydrodynamic parameters using Cooper-Jacob method were: average transmissivity of 5,9x10-3 m²/s and average hydraulic conductivity 2,82x10-4 m/s. The effective porosity is of 15%, obtained by applying Biecinski equation. The potentiometric map shows the main direction of groundwater flow, from west to east, and identifies the recharge areas corresponding to the region of the tablelands of the "Barreiras". The river valleys refer to the discharge areas of the aquifer system. The Recharge was estimated at 253 mm/year, which corresponds to the 16.4% rate of infiltration.

O sistema aquífero Barreiras na região de Parnamirim, RN: uso das águas e potencialidades

The study area is within the Pirangi River Basin, eastern sector of Rio Grande do Norte state, where is located of the Parnamirim city. It has an area of approximately 370 km². Urbanization has developed much fast without an appropriate infrastructure, mainly by the lack of sewage systems, with risks of contamination of groundwater that may cause serious damage to the health of the population. The Barreiras Aquifer System groundwater in the area represents the main source of water supply for urban and rural populations. The use of groundwater occurs without adequate planning and therefore, important recharge areas are being occupied. This study was conducted to quantify the use and evaluation of the potential of groundwater, in order to increase good water quality supply and lower risks of being affected by polluting activities. With these objectives, the following activities were carried out: 268 points of water have been registered; characterization of the lithological, thickness and hydrogeological structure of the Barreiras aquifer, based on the correlation of well logs; and evaluation of hydrodynamic parameters of the aquifer, from the interpretation of results well pumping tests. It was found that the saturated thickness increases from west to east towards the sea, with values ranging from 15,47-56,5 m with an average of 32,45 m. The hydrodynamic parameters using Cooper-Jacob method were: average transmissivity of 5,9x10-3 m²/s and average hydraulic conductivity 2,82x10-4 m/s. The effective porosity is of 15%, obtained by applying Biecinski equation. The potentiometric map shows the main direction of groundwater flow, from west to east, and identifies the recharge areas corresponding to the region of the tablelands of the "Barreiras". The river valleys refer to the discharge areas of the aquifer system. The Recharge was estimated at 253 mm/year, which corresponds to the 16.4% rate of infiltration.

Análise do grau de proteção do Aquífero Barreiras em perímetros sob fertilização química a partir de dados hidrogeofísicos - área da bacia do Rio Catu-RN

The use of chemical fertilization in arable perimeters provides increased productivity, though it can eventually lead to a qualitative depreciation of groundwater sources, especially if such sources are unconfined in nature. In this context, this thesis presents results from an analysis of the level of natural protection of the Barreiras Aquifer in an area located on the eastern coast of the Rio Grande do Norte State - Brazil. Such an aquifer is clastic in nature and has an unconfined hydraulic character, which clearly makes it susceptible to contamination from surface ground loads with contaminants associated with the leaching of excess fertilizers not absorbed by ground vegetation. The methodology used was based on the use of hydro-geophysical data, particularly inverse models of vertical electrical soundings (VES) and information from well profiles, allowing the acquisition of longitudinal conductance cartographies (S), data in mili-Siemens (mS), and the vulnerability of the aquifer. Such maps were prepared with emphasis to the unsaturated overlying zone, highlighting in particular its thickness and occurrence of clay lithologies. Thus, the longitudinal conductance and aquifer vulnerability reveal areas more susceptible to contamination in the northeast and east-central sections of the study area, with values equal to or less than 10mS and greater than or equal to 0,50, respectively. On the other hand, the southwestern section proved to be less susceptible to contamination, whose longitudinal conductance and vulnerability indices are greater than or equal to 30mS and less than or equal to 0,40, respectively.

Análise do grau de proteção do Aquífero Barreiras em perímetros sob fertilização química a partir de dados hidrogeofísicos - área da bacia do Rio Catu-RN

The use of chemical fertilization in arable perimeters provides increased productivity, though it can eventually lead to a qualitative depreciation of groundwater sources, especially if such sources are unconfined in nature. In this context, this thesis presents results from an analysis of the level of natural protection of the Barreiras Aquifer in an area located on the eastern coast of the Rio Grande do Norte State - Brazil. Such an aquifer is clastic in nature and has an unconfined hydraulic character, which clearly makes it susceptible to contamination from surface ground loads with contaminants associated with the leaching of excess fertilizers not absorbed by ground vegetation. The methodology used was based on the use of hydro-geophysical data, particularly inverse models of vertical electrical soundings (VES) and information from well profiles, allowing the acquisition of longitudinal conductance cartographies (S), data in mili-Siemens (mS), and the vulnerability of the aquifer. Such maps were prepared with emphasis to the unsaturated overlying zone, highlighting in particular its thickness and occurrence of clay lithologies. Thus, the longitudinal conductance and aquifer vulnerability reveal areas more susceptible to contamination in the northeast and east-central sections of the study area, with values equal to or less than 10mS and greater than or equal to 0,50, respectively. On the other hand, the southwestern section proved to be less susceptible to contamination, whose longitudinal conductance and vulnerability indices are greater than or equal to 30mS and less than or equal to 0,40, respectively.

Table 1. pH, Temperature, conductivity and hydrochemistry of samples

Carbon dioxide deep geological storage, especially in deep saline aquifers, is one of the preferred technological options to mitigate the effects of greenhouse gases emissions. Thus, in the last decade, studies characterising the behaviour of potential CO2 deep geological storage sites along with thorough safety assessments have been considered essential in order to minimise the risks associated with these sites. The study of natural analogues represents the best source of reliable information about the expected hydrogeochemical processes involved in the CO2 storage in such deep saline aquifers. In this work, a comprehensive study of the hydrogeochemical features and processes taking place at the natural analogue of the Alicún de las Torres thermal system (Betic Cordillera) has been conducted. Thus, the main water/CO2/rock interaction processes occurring at the thermal system have been identified, quantified and modelled, and a principle conclusion is that the hydrogeochemical evolution of the thermal system is controlled by a global dedolomitization process triggered by gypsum dissolution. This geochemical process generates a different geochemical environment to that which would result from the exclusive dissolution of carbonates from the deep aquifer, which is generally considered as the direct result of CO2 injection in a deep carbonate aquifer. Therefore, discounting of the dedolomitization process in any CO2 deep geological storage may lead to erroneous conclusions. This process will also influence the porosity evolution of the CO2 storage formation, which is a very relevant parameter when evaluating a reservoir for CO2 storage. The geothermometric calculation performed in this work leads to estimate that the thermal water reservoir is located between 650 and 800 m depth, which is very close to the minimum required to inject CO2 in a deep geological storage. It is clear that the proper characterisation of the features and hydrogeochemical processes taking place at a natural system analogous to a man-made deep geological storage will provide useful conceptual, semi-quantitative and even quantitative information about the processes and consequences that may occur at the artificial storage system.