<p> Aquifer storage and recovery (ASR) is a strategy in which water is injected into an aquifer when it is plentiful and pumped from the aquifer when water is scarce. An impediment to ASR in Florida is leaching of naturally-occurring arsenic from limestone of the Upper Floridan Aquifer System (UFAS) into stored water. The concentration of arsenic in surface water, which serves as the recharge water for many ASR systems, and native groundwater is usually much less than 3.0 &micro;/L. However, data from ASR wells in Florida show that arsenic in recovered water frequently exceeded the 10 &micro;g/L maximum contaminant level (MCL) established by the Environmental Protection Agency and were as high as 130.0 &micro;g/L. The cause of elevated arsenic concentrations is displacement of reduced native groundwater with oxygenated surface water that dissolves arsenic-bearing pyrite in limestone. Although arsenic can be removed from recovered water during final treatment, mobilization of arsenic in the aquifer at levels that exceed the MCL is problematic under federal regulations. </p><p> This dissertation investigated a number of aspects of the ASR/arsenic problem to provide additional insights into the mechanisms of arsenic mobilization and measures that could be taken to avoid or reduce the release of arsenic during ASR operations.</p><p> Chapter 2, involved development of a geochemical model to simulate an ASR system&rsquo;s injection of oxygenated surface water into reduced groundwater to determine whether aquifer redox conditions could be altered to the degree of pyrite instability. Increasing amounts of injection water were added to the storage-zone in a series of steps and resulting reaction paths were plotted on pyrite stability diagrams. Unmixed storage-zone water in wells plotted within the pyrite stability field indicating that redox conditions were sufficiently reducing to allow for pyrite stability. Thus arsenic is immobilized in pyrite and its concentration in groundwater should be low. During simulation, as the injection/storage-zone water ratio increased, redox conditions became less reducing and pyrite became unstable. The result would be release of arsenic from limestone into storage-zone water.</p><p> Chapter 3 examined the importance of maintaining a substantial volume of stored water around an ASR well to prevent recovery of reduced native groundwater to the vicinity of the well. Depleting the stored water and recovering reduced native groundwater would result in dissolution of arsenic-bearing hydrous ferric oxide (HFO) and release of arsenic into water recovered from the ASR well. Injection/recovery volumes for each cycle for each well were tracked to determine if a substantial volume of stored water was maintained for each cycle or if it was depleted so that reduced native groundwater was brought back to the well. Each well was assigned to either the &ldquo;storage zone maintained group&rdquo; where a zone of stored water was established in early cycles and largely maintained through the period of investigation, or the &ldquo;storage-zone depleted group&rdquo; where a zone of stored water was either established in later cycles and/or was depleted during the period of investigation. Graphical and statistical analyses verified that maximum arsenic concentrations for storage-zone maintained wells were nearly always lower in each cycle and declined below the MCL after fewer cycles than those of storage-zone depleted wells.</p><p> Chapter 4 was a mineralogical investigation of cores located at 20 m (ASR core 1), 152 m (ASR core 2), and 452 m (ASR core 3) from operating ASR wells to determine where mobilized arsenic in limestone is precipitated during ASR. If arsenic is precipitated distally, reduced concentrations of elements in pyrite, (iron, sulfur, arsenic, etc.) would be expected in ASR core 1 relative to more distant cores and there would be noticeable changes in appearance of pyrite crystals due to enhanced oxidation. The results showed that mean concentrations of the elements were lowest in ASR core 2, which did not support distal precipitation. However, scanning electron microscopy identified well-defined pyrite framboids only in core 3 while framboids in ASR cores 1 and 2 were less clear and distinct, indicating pyrite oxidation in cores closest to ASR wells.</p><p> Statistical comparison of concentrations of iron, sulfur, and arsenic between the three ASR cores and 19 control cores not subject to ASR, showed that mean concentrations in ASR cores 1 and 2 were statistically similar to concentrations in control cores. This indicated that concentrations in ASR cores 1 and 2 had not been significantly reduced by ASR. The concentrations of elements were higher in ASR core 3 than in ASR cores 1 and 2 and control cores and statistically dissimilar to all but one control core. This indicated natural heterogeneity in core 3 rather than diminution of elements in ASR cores 1 and 2 due to ASR. The statistical analysis supported local precipitation. Once arsenic is mobilized from dissolved pyrite, it is rapidly complexed with precipitated HFO near the well. As long as all of the stored water is not removed during recovery so that reduced native groundwater is brought back to the well, HFO remains stable and complexed with arsenic. The concentration of elements would not have been lowest in ASR core 1 for this reason and because calculations showed that the mass of arsenic removed during recovery events prior to coring was minor compared to the total in limestone surrounding the well. The implications of this are that while large quantities of arsenic are present near the ASR well, only a small percentage may be available for dissolution. Most arsenic occurs with pyrite in limestone, which may insulate it from exposure to oxidized injection water. Water recovered from ASR wells may continue to have low concentrations of arsenic indefinitely because as limestone is dissolved, more pyrite becomes exposed and available for dissolution. </p><p> The primary contribution of this dissertation to understanding and overcoming the arsenic problem in ASR systems is the empirical data developed to support or challenge important ASR/arsenic hypotheses. These data were used to 1) establish that background concentrations of arsenic in groundwater of the Suwannee Limestone were less than 1&micro;g/L, 2) demonstrate that redox conditions necessary for pyrite in limestone to become unstable and dissolve occur when oxygenated surface water is injected into the aquifer, 3) demonstrate that the concentration of pyrite in the Suwannee Limestone is spatially variable to a high degree, 4) support the hypothesis that following injection of oxygenated surface water, pyrite in limestone dissolves and releases arsenic into solution and HFO forms and complexes with the arsenic near the ASR well, 5) propose that only a small percentage of pyrite near an ASR well may be available for dissolution during each cycle because most occurs in the limestone matrix and is isolated from injection water, 6) propose that as a result of the previous conclusion, water recovered from ASR systems may continue to have low concentrations of arsenic indefinitely because as limestone that contains pyrite is dissolved with each cycle, additional pyrite is exposed and is available for dissolution, and 7) support the effectiveness of maintaining a zone of stored water in an ASR well as an effective means of minimizing arsenic in recovered water during ASR.</p>

<p> A geologic map was drafted of the northern Highland Range (1:24,000 scale), rock units defined, and samples of the volcanic units were obtained and analyzed to produce a representative suite of chemical analyses to characterize the range of geochemical variability. The style, relative timing, and orientation of faults and dikes, and the magnitude and variability of stratal tilting was examined to evaluate the structural and magmatic evolution of the northern Highland Range in the context of models for the Colorado River Extensional Corridor and Black Mountains accommodation zone. Methods involved field mapping of the range scale structure and geometry of faulting, structural interpretation, and geochemical analysis of ten representative samples by X-ray spectrometry. Structural data was interpreted with stereonets; geochemical whole rock, and major elemental data was analyzed by comparing elemental oxides; trace elemental data was analyzed by normalizing to chondrite concentrations. The northern Highland Range is a ca. 3,000 m-thick sequence of volcanic and volcaniclastic flows and breccias overlain by regionally extensive tuffs (Mt. Davis and Bridge Spring). Unique mineralogy, geochemistry and lithologic character of some units and volcanic vent facies, as well as the presence of domes and dikes feeding the extrusives argue for local derivation from a dome/stratocone volcanic complex that was mostly restricted to the northern Highland Range. </p>

<p> In this study, we conduct high-pressure (HP) high-temperature (HT) diffusion experiments in anhydrous rhyolite near 1000 &deg;C and 1100 &deg;C at 100 MPa using the cold seal pressure apparatus to diffuse argon into natural obsidian charges. We use electron microprobe measurements of the argon concentration gradients to calculate the argon diffusivity <i>(D_Ar)</i> as a function of temperature and pressure. The range and mean of <i> D_Ar</i> calculated from these measurements are in good agreement with previous studies (Carroll 1991, Behrens and Zhang 2001). Even so, we observe significant variability in our <i>D_Ar</i> results, beyond what is likely due to analytical or experimental uncertainty; nearly as much variability as Carroll (1991) and Behrens and Zhang (2001) reported. In particular, we notice a small systematic geometric bias in the distribution of argon in our samples, which appears to correlate with sample deformation. We attribute this effect to distortion of concentration gradients by viscous advection.</p>

Thesis (Ph.D.)--Indiana University, Dept. of Geological Sciences, 2005. / Source: Dissertation Abstracts International, Volume: 67-01, Section: B, page: 0146. Adviser: Edward M. Ripley. "Title from dissertation home page (viewed Feb. 9, 2007)."

Thesis (M. Sc.)--University of Queensland, 2003. / Includes bibliographical references.

<p> The abstract is not available from PDF copy and paste.</p>

<p> The eastern Willouran Ranges and northern Flinders Ranges, South Australia contain Neoproterozoic and Cambrian outcrop exposures of diapiric breccia contained in salt diapirs, salt sheets and associated growth strata that provide a natural laboratory for testing and refining models of salt-sediment interaction, specifically allochthonous salt initiation and emplacement and halokinetic deformation. Allochthonous salt, which is defined as a sheet-like diapir of mobile evaporite emplaced at younger stratigraphic levels above the autochthonous source, is emplaced due to the interplay between the rate of salt supply to the front of the sheet and the sediment-accumulation rate, and may be flanked by low- to high-angle stratal truncations to halokinetic folds. Halokinetic sequences (HS) are localized (&lt;1000 m) unconformity-bound successions of growth strata adjacent to salt diapirs that form as drape folds due to the interplay between salt rise rate (R) and sediment accumulation rate (A). HS stack to form tabular and tapered composite halokinetic sequences (CHS), which have narrow and broad zones of thinning, respectively. The concepts of CHS formation are derived from outcrops in shallow water to subaerial depositional environments in La Popa Basin, Mexico and the Flinders Ranges, South Australia. Current models for allochthonous salt emplacement, including surficial glacial flow, advance above subsalt shear zones and emplacement along tip thrusts, do not address how salt transitions from steep feeders to low-angle sheets and the model for the formation of halokinetic sequences has yet to be fully applied or tested in a deepwater setting. Thus, this study integrates field data from South Australia with subsurface data from the northern Gulf of Mexico to test the following: (1) current models of allochthonous salt advance and subsalt deformation using structural analysis of stratal truncations adjacent to outcropping salt bodies, with a focus on the transition from steep diapirs to shallow salt sheets in South Australia; and (2) the outcrop-based halokinetic sequence model using seismic and well data from the Auger diapir, located in the deepwater northern Gulf of Mexico. Structural analysis of strata flanking steep diapirs and allochthonous salt in South Australia reveals the transition from steep diapirs to shallowly-dipping salt sheets to be abrupt and involves piston-like breakthrough of roof strata, freeing up salt to flow laterally. Two models explain this transition: 1) salt-top breakout, where salt rise occurs inboard of the salt flank, thereby preserving part of the roof beneath the sheet; and 2) salt-edge breakout, where rise occurs at the edge of the diapir with no roof preservation. Shear zones, fractured or mixed `rubble zones' and thrust imbricates are absent in strata beneath allochthonous salt and adjacent to steep diapirs. Rather, halokinetic drape folds, truncated roof strata and low- and high-angle bedding intersections are among the variety of stratal truncations adjacent to salt bodies in South Australia. Interpretation and analysis of subsurface data around the Auger diapir reveals similar CHS geometries, stacking patterns and ratios of salt rise and sediment accumulation rates, all of which generally corroborate the halokinetic sequence model. The results of this study have important implications for salt-sediment interaction, but are also critical to understanding and predicting combined structural-stratigraphic trap geometry, reservoir prediction and hydrocarbon containment in diapir-flank settings.</p>

Thesis (PH.D.) -- Syracuse University, 2007. / "Publication number AAT 3266307"

Thesis (M.S.)--Oregon State University, 1988. / Typescript (photocopy). Mounted photographs. Plates in pocket. Includes bibliographical references (leaves 290-308). Also available via the World Wide Web.

Thesis (Ph. D.)--University of Melbourne, 1996. / Includes bibliographical references.