Browsing by Subject "Groundwater"

Arsenic (As) exposure via groundwater consumption is a global health problem affecting millions. Monitoring exposure is a key step in understanding and predicating future health outcomes. This thesis explores the relationships between arsenic concentrations in toenails and arsenic in water. Three case studies were investigated, with residents from: North Carolina, USA (n=103); the Rift Valley, Ethiopia (n=60); and the Mekong Delta, Vietnam (n=65). Arsenic concentrations above the WHO's recommended 10ppb limit were found in groundwater from the three research sites.

Arsenic in toenails was analyzed by inductively coupled plasma mass spectrometry (ICP-MS).

In the Rift Valley of Ethiopia, 53% of the tested drinking wells (n=34) had As above the WHO's limit. Arsenic concentrations in toenails (n=60) were significantly correlated to As concentrations in groundwater (r=0.72; p<0.001), reflecting the direct exposure of rural communities to As in well water, which is their principle water source. Male minors (<18 years old) were found to have greater nail-As concentrations compared with adults consuming equal amounts of As (p<0.05). Estimated As dose specifically from drinking water sources was also associated with nail concentrations (p<0.01).

In the Mekong Delta of Vietnam (Dong Thap Province), 36 out of the 68 tested wells had As content above the WHO's recommended limit of 10ppb, with levels as high as 981 ppb. Arsenic contents in nails collected from local residents (n=62) were significantly correlated to As in drinking water (r=0.49, p<0.001). Demographic and survey data show that the ratio of As in nail to As in water varies among residents that reflects differential As accumulation in the exposed population. The data show that water filtration and diet, particularly increased consumption of animal protein and dairy and reduced consumption of seafood, were associated with lower ratios of As in nail to As in water and thus could play important roles in mitigating As exposure.

Sixty-one wells were tested from Union County, North Carolina, with 15 out of 61 wells exceeded the WHO's 10 ppb limit. Arsenic values ranged from below the limit of detection (0.07) to 130ppb, with a mean of 11ppb (median=1.5ppb). Nails were collected from county residents (n=103) and were statistically correlated with As-water concentrations (r=0.48, p<0.001).

Integration of the data from the three cases studies across different populations and ethnicities show high correlation between As concentrations in groundwater and As in nails in all the three locations (r(Union County)= 0.48, p<0.001; r(Ethiopia)=0.72 p<0.001; r(Vietnam)=0.49, p<0.001). For As-nail to As-water pairs in which As in water was above 1ppb, these three locations are statistically indistinguishable from one another (r=0.62, p<0.001, n=176). These results support the hypothesis that nails can be used as a biomarker of exposure regardless of geographic or ethnic differences in populations considered. Nutrition (meat, seafood, and milk consumption) rather than gender, ethnicity, or dose is suggested to be the major confounding issue affecting the magnitude of As exposure in the human body.

Prior studies of groundwater systems have associated increasing salinity and anoxic conditions with increasing radium (Ra) activities in water due to the decreasing effectiveness of Ra removal processes. However, the components of salinity (e.g. Ca vs. Na and SO₄^2- vs. Cl^--dominated waters), and the relative importance of salinity-sensitive vs. redox-sensitive processes for Ra mobilization, are less well understood. In this research, the response of Ra to hydrochemical change was examined using a multiple tracer approach to obtain detailed information on divalent cation and Ra mobility. A range of salinity and redox conditions was examined in five field-based studies in the United States and Morocco: (1) fresh waters in fractured crystalline rocks in the Piedmont region of North Carolina; (2) the Willcox Basin, an oxic alluvial basin-fill aquifer in southeastern Arizona; (3) the Jordan sandstone aquifer, a carbonate-cemented quartz sandstone in southeastern Minnesota; (4) an unconfined coastal aquifer undergoing salinization in the city of Agadir, Morocco; and (5) the confined, fresh to saline Cretaceous and Pliocene aquifers of the Atlantic Coastal Plain in North Carolina.

In addition to analysis of major element concentrations, trace metal concentrations, and ²²⁴Ra, ²²⁶Ra, and ²²⁸Ra activities, complementary isotope systems were applied to gain insights on the relative stability of chemical processes that remove radium and other alkaline earth metals: (1) strontium isotope ratios (⁸⁷Sr/⁸⁶Sr) trace divalent cation release from sources such as clay and carbonate minerals in the aquifer solids and also indicate conditions in which divalent cation release (rather than uptake) is dominant; (2) boron concentrations and isotopes (δ¹¹B) coincide with the opposite condition in freshening conditions of the Atlantic Coastal Plain, in which divalent cations are removed in exchange for Na; and (3) sulfur and oxygen isotopes (δ³⁴S, δ¹⁸O) of sulfate trace sulfate sources and provide information on sulfate-reducing conditions, which can inhibit barite (BaSO₄) from removing Ra by coprecipitation. In addition, other isotopic and ion measurements trace salinity sources and groundwater residence time, including δ²H, δ¹⁸O, ³H, Br^-/Cl^-, Na/Cl^-, and Ca/Na.

This dissertation documents correlations between salinity and radium in the brackish to saline North Carolina coastal plain aquifer with total dissolved solids (TDS) up to ~18,000 mg L^-1 and to some degree in the Moroccan coastal aquifer, but even the lower-salinity waters (TDS <3000 mg L^-1) exhibit a range of Ra activities spanning approximately 3 orders of magnitude. Among these low-TDS waters, the highest Ra activities were observed in the anoxic Jordan sandstone aquifer and the lowest were observed in the oxic Willcox Basin aquifer. Although the main control on radium activities in fresh groundwater is the U- and Th-series radionuclide content of the aquifer solids, important secondary controls include the stability of redox-sensitive radium adsorption sites (Mn and Fe oxides), the relative dominance of divalent vs. monovalent cations (e.g. the Ca/Na ratio), formation of the uncharged RaSO₄⁰ complex, and/or the saturation state with respect to barite. These processes interact in varied ways in the field-based studies. Increasing radium activities and decreasing ²²²Rn/²²⁶Ra ratios in the North Carolina fractured crystalline rock groundwater system are correlated with increasing Ba, Mn, and Fe concentrations and decreasing dissolved oxygen concentrations, related to weathering and/or organic carbon oxidation. Radium activities in the oxic, neutral to slightly basic Willcox Basin are very low (median ²²⁶Ra activity 2 mBq L^-1), probably due to a combination of effective Ra removal processes including adsorption to Mn and/or Fe oxides and the overall removal of divalent cations during groundwater evolution in this system. These are the same surface charge conditions that release arsenic, of regional water concern, in this pH range. Radium in Jordan aquifer groundwater is dependent on local variations in solid-phase radionuclide levels, probably hosted in the carbonate cement phase. Also, Ra is inefficiently adsorbed to the aquifer solids in the aquifer's anoxic conditions, resulting in the highest radium levels reported in this dissertation (²²⁶Ra up to 420 mBq L^-1) despite apparent barite precipitation that partially removes Ra. Radium-224 activity in the Moroccan coastal aquifer is associated with salinity, but Ra overall is apparently controlled by barite, indicated by conditions near BaSO₄ saturation. Radium activity in the saline waters of the Atlantic Coastal Plain aquifers is associated with TDS concentrations, but the cation exchange properties of the aquifer may provide a major mechanism of Ra removal in the Na-HCO₃^- and Na-Cl^- waters. Overall, the complex interaction between groundwater chemistry and Ra-removing processes implies that in waters with TDS below approximately 3,000 mg L^-1, dissolved solids concentration alone does not fully describe radium's response to hydrochemical conditions, but rather that aquifer-specific examination of Ra removal mechanisms is needed.

Groundwater has an important role in forging the composition of surface water, supplying nutrients crucial for the development of balanced ecosystems and potentially introducing contaminants into otherwise pristine surface water. Due to water-rock interactions radium (Ra) in groundwater is typically much more abundant than in surface water. In saline environments Ra is soluble and is considered a conservative tracer (apart for radioactive decay) for Ra-rich groundwater seepage. Hence in coastal environments, where mostly fresh groundwater seep into saline surface water, Ra has been the prominent tracer for tracking and modeling groundwater seepage over more than three decades. However, due to its reactivity and non-conservative behavior, Ra is rarely used for tracing groundwater seepage into fresh or hypersaline surface water; in freshwater, Ra is lost mostly through adsorption onto sediments and suspended particles; in hypersaline environments Ra can be removed through co-precipitation, most notably with sulfate salts.

This work examines the use of Ra as a tracer for groundwater seepage into freshwater lakes and rivers and into hypersaline lakes. The study examines groundwater-surface water interactions in four different environments and salinity ranges that include (1) saline groundwater discharge into a fresh water lake (the Sea of Galilee, Israel); (2) modification of pore water transitioning from saline to freshwater along their flow through sediments (pore water in sediments underlying the Sea of Galilee, Israel); (3) fresh groundwater discharge into hypersaline lakes (Sand Hills, Nebraska); and (4) fresh groundwater discharge into a fresh water river (Neuse River, North Carolina). In addition to measurement of the four Ra isotopes (226Ra, 228Ra, 223Ra, 224Ra), this study integrates geochemical (major and trace elements) with additional isotopic tools (strontium and boron isotopes) to better understand the geochemistry associated with the seepage process. To better understand the critical role of salinity on Ra adsorption, this study includes a series of adsorption experiments. The results of these experiments show that Ra loss through adsorption decreases with increasing salinity, and diminishes in salinity as low as ~5% of the salinity of seawater.

Integration of the geochemical data with mass-balance models corrected for adsorption allows estimating groundwater seepage into the Sea of Galilee (Israel) and the Neuse River (North Carolina). A study of the pore water underlying the Sea of Galilee shows significant modifications to the geochemistry and Ra activity of the saline pore water percolating through the sediments underlying the lake. In high salinity environments such as the saline lakes of the Nebraska Sand Hills, Ra is shown to be removed through co-precipitation with sulfate minerals, its integration into barite (BaSO₄) is shown to be limited by the ratio of Ra:Ba in the precipitating barite.

Overall, this work demonstrates that Ra is a sensitive tracer for quantifying groundwater discharge even in low-saline environments. Yet the high reactivity of Ra (adsorption, co-precipitation, production of the short-lived isotopes) requires a deep understanding of the geochemical processes that shape and control Ra abundances in water resources.

Ephemeral and intermittent streams comprise the majority of stream channel length worldwide. These non-perennial streams are important landscape features in that they transport materials and solutes from the terrestrial landscape to downstream aquatic systems, provide unique ecological habitats, and transmit, transform, and retain chemical species. Although these streams serve a myriad of hydrological and biogeochemical functions, the mechanisms that drive runoff generation as well as the hydrological and biogeochemical contributions of these non-perennial streams to downstream perennial stream systems are poorly understood. To address this knowledge gap, this dissertation focused on investigating dominant runoff sources, flowpaths, and stream-groundwater interactions across an ephemeral-to-perennial drainage network located in the humid Piedmont landscape of the Duke Forest, North Carolina, USA. Not only does this research work to fill an important knowledge gap, but it was conducted in a low relief landscape, which is a highly understudied landscape type.

A 48.4 hectare research watershed was designed, fully instrumented, and continuously managed to address the objectives of this dissertation. Through this, the timing and magnitude of precipitation, runoff, and the dominant runoff generating flowpaths were monitored across watershed scales at 5 minute intervals for two years. In the first chapter of this dissertation, observations of hydraulic gradients between groundwater and the stream were used to show event- and seasonal-driven bidirectional flow between these two systems. The results of this work indicated that non-perennial headwater streams can both lose to and gain water from the deep groundwater system. Calculations from an annual water balance in the headwater catchment confirmed this temporally shifting flow system that resulted in significant annual stream water loss to the groundwater system. In the second chapter, a data-driven visualization of the bidirectional stream-groundwater interactions across a characteristic hillslope that built on Chapter 1 results was presented. This animation and supporting text provided visualization of a shallow, perched, transient water table that drove runoff generation during periods of losing stream gradients. Chapter 3 built on these results through introduction of a conceptual model of the dominant runoff generating processes in this headwater catchment during ephemeral and intermittent runoff regimes. This chapter focused on two intensively sampled precipitation events to demonstrate that distinct runoff generating mechanisms dominate runoff regimes across different catchment storage states. Finally, in the fourth chapter, observations of dissolved organic carbon fluxes, runoff contributions, active surface drainage network length, and groundwater across different landscape elements (headwaters and lowlands), were used to investigate the balance of longitudinal, lateral, and vertical runoff processes on runoff and carbon export dynamics across watershed scales. Overall, these findings shed light on dominant runoff generation mechanisms in low relief, highly weathered landscapes, which are a globally understudied landscape type. These findings also fill a knowledge gap about the mechanisms that drive runoff generation and stream-groundwater interactions surrounding non-perennial streams and the resulting influences on carbon and water fluxes in downstream, perennial waterways.

Clean water is a critical natural resource. We do not have much available: only 2.5% of water on Earth is freshwater and of that only 31% is in liquid form. 96% of the liquid fresh water is groundwater. Unfortunately that resource is subject to contamination by hazardous materials accidentally or illicitly spilled, leaked, or deposited in or on the ground. Among the methods to remediate these disasters, pump-and-treat (P&T) is the most common. The vertical circulation well (VCW) is a P&T configuration with extraction and injection sites within the same well. It can be adapted to many remediation techniques and has been gaining popularity since the 1990s and is often a better alternative to conventional P&T. Conventional P&T and VCWs are typically run with steady flow.

The major bottleneck to steady flow remediation is that contaminants become trapped in dead-end pores. In an aquifer there are two types of pores: pass-through pores and dead-end pores. The flow in former completely sweeps through the pore space while the flow does not enter the later; however, the flow through the pass-through pore induces a vortex in the dead-end pore. Under steady flow the only mechanism for contaminants to escape the dead-end pores is molecular diffusion.

A similar problem is encountered in the removal of surfactants in the manufacture of semiconductor and the removal of oil residue build-up in small ducts. Manufacturers discovered that pulsed flow would accelerate the mass transfer between the cavities and grooves on these surfaces and the external flow. This was because the unsteady ramp-up in flow rate initiated a deep sweep of the cavities. The unsteady ramp-down in flow rate initiated a vortex ejection where the sequestered vortex is no longer constrained and protrudes from the cavity.

We hypothesized that just as pulsed flow improves cleaning of grooved surfaces in several manufacturing procedures, rapidly pulsed pumping (with a period on the order of a second rather than weeks or months) in pump-and-treat groundwater remediation would boost the diffusion-limited removal of contaminants trapped in dead-end pores by generating transient deep sweeps and vortex ejections in these pores. These processes have not yet been exploited in groundwater remediation to any significant degree.

We tested our hypothesis in a series of numerical and laboratory experiments. We considered unwashed and washed media. For unwashed media (Chapter 1) we used as a square pore in the numerical domain and crushed glass (for its negligible sorption capacity) in laboratory column studies. For washed media (Chapter 2) we used a smooth dead-end pore constructed with two tangential quarter circles as the pore in the numerical domain and glass spheres in the laboratory column studies. In all our laboratory experiments we used a fluorescent dye, Fluorescein, as a conservative tracer. We used the same parameters in our numerical experiments. However, in some we also considered immiscible contaminants such as NAPLs (Chapter 4).

All numerical experiments were conducted with the computational fluid dynamics software, FIDAP. In numerical experiments we studied the contaminant removal from interacting dead-end pores connected to both a straight pass-through pore and a divergent pass-through pore. The latter with the flow somewhat analogous to the radial spreading encountered around a around a well in field applications (Chapter 5).

To elucidate the dead-end pore dynamics (Chapter 3), we performed numerical experiments and used a physical model to obtain a relationship between the rapidly pulsed flow frequency and length of the pore. Our dimensional analysis pointed to the change in pressure as the key component in the initiation of transient deep sweeps and vortex ejections, two new pore-cleaning mechanisms.

We conclude that the rapidly pulsed flow improves the recovery of contaminants from unwashed, or rough, porous media. In numerical experiments with a pore system consisting of just a single square dead-end pore and a single pass-through pore, at 100 pore volumes pumped the rapidly pulsed flow improved cleanup of the dead-end pore alone by approximately 40%. This translates into a 10% improvement of the cleanup of the pore system (dead-end and pass-through pore). Since the dead-end pore is the bottleneck of the current groundwater remediation, it the first measure that is relevant.

In corresponding laboratory column experiments with crushed glass, the dead-end pore volume alone is not known. The cleanup of the whole pore space was improved by roughly 10% with the rapidly pulsed pumping, which corresponds nicely to our numerical results.

Our numerical experiments demonstrate that there exists an optimal pulsed pumping frequency that is a function of the local flow velocity and the pore geometry (size and morphology).

The contaminant recovery from washed, or rounded, media was not as pronounced in the laboratory experiments and the numerical experiments showed no improvement. While both rapidly pulsed and steady flow recovered all of the contaminant in the laboratory column tests, the difference in the time between the two pumping schemes was approximately 0.9 pore volumes pumped. This improvement is likely to be amplified with sorbing contaminants.

Many contaminants are non-aqueous phase liquids (NAPLs), which do not readily dissolve in water. We showed in numerical experiments that rapidly pulsed flow can recover NAPLs with viscosity lower than water, but is not as effective with higher viscosity materials; however, these results were based on a model that did not account for interfacial tension and wetting; therefore we will require additional numerical and laboratory experiments.

In practice, a flow through porous media is significantly more complex than the one-directional dominated flows considered in our numerical and laboratory column experiments. Around a well the flow is typically three-dimensional and largely radially dominated. We constructed two numerical domains to study the interactions between the cleanup of three square pores: one in a straight channel and one in a divergent channel to study the radial spread that would be experienced around a well. For a series of three dead-end pores, there was a 35% improvement by rapidly pulsed flow over steady flow in the straight channel and a 33% improvement in the divergent domain. The optimal frequency was different in the divergent flow even though the pores were the same size as in the previous study. Since the divergent channel reduced the flow velocity, the pulses reached the pores at a decreasing rate. Due to this divergence and the range of pore-sizes in a natural aquifer, implementation of rapidly pulsed flow should likely include a range of frequencies.

We concluded that the rapidly pulsed flow on the time scale of one-second would greatly enhance the cleanup of contaminated aquifers by P&T or VCW approaches. We measured significant improvements in the time to recovery. For our preliminary VCW experiment showed that rapidly pulsed pumping recovers 50% of the contaminant four times faster than steady pumping. P&T and VCW remediation typically use a steady flow; there are some methods that change the flow rate in P&T and other configurations, such as the VCW. These periodic changes in rate are on the scale of months to years. Some VCWs and air sparging technologies pulse oxygen, surfactants, and/or nutrients into the aquifer to oxidize, mobilize, or bioremediate the contaminants. As reviewed in chapter 6 in detail, all pulsing so far applied in remediation is on the time scale of a day or longer. Such low pulsing frequency does not produce sufficiently many deep sweeps to make a significant difference in cleaning dead-end pores.

Implementation of rapidly pulsed technology will utilize the same extraction and injection wells currently used in pump-and-treat remediation but will require replacement or significant modification of the pumps.

There are public health and financial implications of this research. In the dissertation conclusions section we reinterpret our numerical experiments with the multiple interacting dead-end pores and a divergent pass-through pore and laboratory experiments with a vertical circulation well chamber by calculating and plotting the ratio of times needed to reach a specified fraction recovered (specified cleanup level) in the steady and rapidly pulsed pumping modes, \tau_{s} / \tau_{p}. This ratio represents the speedup factor, i.e., the factor by which the time needed to reach the specified cleanup level with the conventional remediation (with steady pumping) would be reduced. From our experiments it appears that with the increasing level of targeted cleanup (contaminant fraction recovered), the speedup factor increases and may even exceed an order of magnitude. As we demonstrate in the dissertation conclusions section, this could translate into tens of billions of dollars in savings. Whether or not the laboratory speedup factors would hold in the field cannot be established without field-scale experiments.