Browsing by Author "Sutton, Sally, committee member"
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Item Open Access Alteration of organic matter and copper mineralization in the Midcontinent Rift, USA(Colorado State University. Libraries, 2017) Schultz, Max, author; Ridley, John, advisor; Sutton, Sally, committee member; Kennan, John, committee memberTo view the abstract, please see the full text of the document.Item Open Access Analysis of contaminant mass in place in transmissive and low-k zones(Colorado State University. Libraries, 2020) Roads, Eric, author; Sale, Tom, advisor; Sharvelle, Sybil, committee member; Sutton, Sally, committee memberContaminant hydrology has been challenged by the common perception of homogeneous subsurface media. Previous sampling methods neglect the importance of differentiating between transmissive and low-k zones. Cryogenic core collection is a high-resolution sampling technique that can highlight the occurrence of transmissive and low-k zones as well as the distribution of contaminants in transmissive and low-k zones. Cryogenic core collection uses a CSU patented process that preserves core samples downhole using liquid nitrogen. Frozen cores are shipped to CSU on dry ice and always kept at -80ᵒC. Cores are cut into subsamples and analyzed to determine geology, physical properties, contaminant concentrations, and microbial ecology. The data is processed into Excel™ and then stored in gINT™, a relational database. Herein, consideration is given to 390 feet of collected core from 31 boreholes from 5 hydrocarbon and 2 chlorinated solvent sites. Data analyses include comparisons within a site, intra-site comparisons, and between sites, inter-site comparisons. Tools are developed in gINT™ to automate transformation of collected data into vibrant visual graphical outputs. First, for every borehole, a graphic is generated that includes a comprehensive panel of geology, contaminants of concern and fluid saturations properly presented by depth. Building on this, distributions of contaminants as a function of transmissive or low-k zones are resolved. Lastly, key attributes of mass distribution are compared across individual sites (intra-site comparisons) and between sites (inter-site comparisons). Our analysis presents a first-ever quantification of distribution of contaminant mass in transmissive and low-k zones. The analysis begins with processing concentration data-by-depth to produce the total mass of contaminants in each borehole, the mass of contaminants in transmissive zones, and the mass of contaminants in low-k zones. The contaminant mass in a borehole is presented for each contaminant individually and as sum of all contaminants. The visualization of this data is not intuitive due to the ranges of contaminant mass in place. Hydrocarbons contaminated sites have contaminant masses that range from less than half a kilogram to about 30 kilograms of contaminants per m2. Chlorinated solvent contaminated sites have contaminant masses that vary from less than 240 micrograms to right under 2.5 kilograms of contaminants per m2. The data is processed such that boreholes and sites with broad ranges of conditions can be compared. Data is presented as percent of contaminant mass in transmissive zones by borehole; the percent of contaminant mass in low-k zones by borehole, the percent of borehole that is transmissive, and percent of borehole that is low-k. Unlike previous data that required a y-axis formatted to a log scale, this data is visualized on a plot with the y-axis set at 0-100%. The fraction of a borehole that is low-k ranges between 0% and 94% with a median value of 52%. Secondly, the fraction of total contaminant mass stored in low-k zone ranges from 1% to 96% with a median value of 46%. Illustrations of the tendency for mass storage in low-k zones are presented through difference in percent of borehole that is low-k and percent of contaminants in a borehole in low-k zones. The calculations defined a positive difference as preference for transmissive zones and a negative difference as preference for low-k zones. Data presented characterized the 18 hydrocarbon contaminated boreholes, 12 chlorinated solvent contaminated boreholes, and all 30 contaminated boreholes respectively. Key insights include • Hydrocarbon contaminated boreholes showed statistically significant preference for low-k zones if the unit difference of percent of borehole that is low-k and percent of contaminants in a borehole in low-k zones was less than -24%. • Chlorinated solvent contaminated boreholes showed statistically significant preference for low-k zones if the unit difference of percent of borehole that is low-k and percent of contaminants in a borehole in low-k zones was less than -11%. • Remediated chlorinated solvent boreholes presented a preference for low-k zones where their non-remediated counterparts showed preference for transmissive zones. • All contaminated boreholes showed statistically significant preference for low-k zones if the unit difference of percent of borehole that is low-k and percent of contaminants in a borehole in low-k zones was less than -19%. • As an example, this thesis provides a unique documentation of benzene persisting in low-k zones. The presence or absence of benzene in low-k zones will have a large implication with respect to the longevity of benzene in monitoring wells and the efficacy of remedial measures that address the longevity of benzene in monitoring wells. Overall, cryogenic core collection and advanced analytics provides a practical means of quantifying contaminant occurrence in transmissive and low-k zones and an improved basis for anticipating the benefits of site remedies.Item Open Access Characterization and comparison of flowback/produced water of fresh water to recycled water stimulated wells and the subsequent evaluation of the influence of inorganic ions on fracturing fluid viscosity(Colorado State University. Libraries, 2016) White, Shane A., author; Carlson, Kenneth, advisor; Catton, Kimberly, committee member; Sutton, Sally, committee memberAs the Oil and Gas Industry begins to recycle flowback and produced waters, new challenges arise in using recycled water as a base fluid (fluid for hydrating gel) for future hydraulic fracturing operations. By understanding water qualities at all steps of the water life cycle in recycled operations, it is possible to improve treatment effectiveness and efficiency as well as make informed decisions on future fracturing fluid designs. This thesis contains two studies. The first study looks to determine water qualities, their differences and similarities, among multiple wells in the same Basin. These wells were fractured using a variety of techniques such as varied recycled to fresh water blends and fluid designs. The collection and water quality analysis of roughly 150 samples from seven wells on two different sites showed that there is little difference in water quality between wells fractured with recycled water (recycled wells) and wells fractured with fresh water (fresh wells). The study does not find noticeable differences in dissolved ionic concentrations between fresh and recycled wells. However, recycled wells located on the first site show emulsified oils in flowback. This can be observed with increased total organic carbon loadings of 12,170mg/l for day three flowback of one recycled well in comparison to 3,268mg/L for day three flowback of a fresh well. Treatment effectiveness was also correlated with emulsified oil concentrations and as their concentrations decreased, so did the coagulant dose required for optimum treatment. Spatial variation was observed between the two sites. Although the concentration of varying inorganics between the two locations was observable, temporal trends were consistent between wells. The second study provides data that can be used in decision making for future fracturing fluid design and development. By observing the effect individual ions and ion combinations have on fracturing fluid stability, operational limits were determined for two fracturing fluids employed by operators in the DJ Basin. Theoretical mechanisms of action were determined for the factors that influence fracturing fluid stability. Specific cations compete for crosslink sites on the gel polymer through shielding or by competitively complexing with active sites that the added crosslinker would normally complex with, resulting in a less stable fluid. Hydrogen bonds can sometimes form bonds at active sites and make a weak crosslink. At lower concentrations calcium and magnesium can replace these weaker crosslinks with stronger bonds, creating a more stable fluid.Item Open Access Development of a GIS based tool to analyze produced water from oil and gas wells and prediction of equilibrium concentrations using CalcAQ(Colorado State University. Libraries, 2013) Dhanasekar, Ashwin, author; Carlson, Kenneth H., advisor; Arabi, Mazdak, committee member; Sutton, Sally, committee memberNew extraction techniques based on hydraulic fracturing and horizontal drilling have significantly increased the available oil and gas in the United States. Producing oil and gas from shale formations is the main source of these unconventional resources. When shale formations are hydraulically fractured to increase the permeability, up to 5 million gallons of water can be used for each well. The significant use of water has caused concerns by several stakeholders, particularly in regions that are constantly facing water shortages such as Texas or Colorado. After the well is fractured, large amounts of water return as frac flowback and then after the well is put into production, water that is coproduced with oil and gas must be collected for the life of the well. The produced water has hazardous characteristics since it has been in contact with oil and gas for millions of years and disposal or reuse is an important part of an oil and gas operation. Current water management for produced water includes underground injection and surface disposal or reuse. Owing to a large amount of total dissolved solids (TDS), metals and hydrocarbons (e.g. BTEX) in the produced water, the brine needs to be treated to achieve acceptable water quality for subsequent disposal or reuse. Reusing and recycling of produced water for drilling and fracturing after appropriate treatment has multiple advantages including less truck traffic and lower fresh water demands. The objective of the research in this thesis was to integrate the OLI chemical equilibrium model into the OWM (Optimized Water Management) tool framework to allow chemical equilibrium calculations to be made for each well and in the aggregate throughout the Wattenberg oil and gas field of northern Colorado. The calculations from this model can then be used as design criteria for treatment train definition based on the desired water disposal outcome. OLI Systems software was developed for the chemical and oil and gas industry and is well suited as a module for calculating chemical equilibrium values for produced water and frac flowback water. The research described in this thesis includes predictions of equilibrium chemistry, solids precipitation and scale forming index, based on water quality data collected in the field. The model can also predict requirements for combining and treating produced water streams to achieve process objectives. At the same time, water quality will be analyzed after detailed sampling from various parts of the field. Finally, water quality after precipitation, settling and filtration has been used to estimate the osmotic pressure and design reverse osmosis processes for different levels of TDS rejection. This will be integrated with a customized ArcGIS tool that will help in predicting treatment specifics on a spatial scale.Item Open Access Enhancing oleophilic biobarriers for non-tidal sediments impacted with petroleum hydrocarbons(Colorado State University. Libraries, 2021) DeBiasi, Marina Ann, author; Scalia, Joseph, IV, advisor; Sale, Tom, advisor; Sutton, Sally, committee memberThe objective of this study is to develop tools to prevent petroleum hydrocarbons trapped in non-tidal sediments from causing detrimental effects such as sheens. Oleophilic biobarriers (OBBs) provide a robust, low-cost solution for managing petroleum hydrocarbon contamination at groundwater-surface water interfaces in tidal zones but are untested in non-tidal zones. This study evaluates enhanced OBB remedies for petroleum hydrocarbon contamination in non-tidal zones by incorporating amendments within the OBB. The amended OBB is intended to serve as an engineered bioremediation tool to enhance microbial growth and degradation of petroleum hydrocarbons by supplying the system with a resource of electron donors and nutrients while simultaneously mitigating petroleum hydrocarbon releases to surface water. Complementary laboratory and field studies were conducted to test non-tidal OBBs (NOBBs) with six amendment types: (1) hematite (H), (2) greensand (GS), (3) greensand + hematite (GS+H), (4) gypsum (GYP), (5) hematite + greensand + gypsum (ALL), and (6) blank (B). The laboratory study was constructed as a series of chemostats using sediment and water samples from the field site. This study observed the productivity of petroleum hydrocarbon degradation through biweekly headwater extractions analyzing alkalinity, dissolved inorganic carbon (DIC), and pH as well as continuously monitored oxidation reduction potential (ORP). Results from these tests indicated that the GYP amendment was most effective in degrading petroleum hydrocarbons while the B and ALL amendments were least effective. However, all systems exhibited increased effluent DIC characteristic of enhanced petroleum hydrocarbon degradation. The field study was constructed as a series of OBB disks deployed atop petroleum hydrocarbon impacted sediments in a non-tidal setting. Results from the laboratory and field study illustrated abundant microbial growth after six months. The NOBBs with the top three highest numbers of microbial abundance were found in the field (F): F-GS+H, F-B, and F-GS. The overall results of both lab and field studies suggest that NOBBs, whether amended or not, provide effective media for petroleum hydrocarbon-degrading microorganisms. This study illustrates the promise of the non-tidal OBB as a bioreactive barrier for petroleum hydrocarbon impacted sediments. Further study is needed to evaluate the rate of petroleum hydrocarbon degradation in a non-tidal OBB relative to the rate of loading.Item Open Access False Bakken' interval- sediment patterns and depositional architecture at the facies boundary between siliciclastic mudstones and carbonates, Lodgepole Formation, Mississippian in the Williston Basin, ND(Colorado State University. Libraries, 2020) Spansel, Joel, author; Egenhoff, Sven, advisor; Sutton, Sally, committee member; von Fischer, Joe, committee memberThe lateral facies transition on deep shelves between carbonates and siliciclastic mudstones is largely enigmatic. Based on detailed facies descriptions and interpretations, this study explores which processes have shaped the sedimentary rocks on both sides of this lithological divide, and adds to our understanding of processes operating on deep shelves in general. Both siliciclastic and carbonate rocks of the 'False Bakken' and 'Scallion' intervals of the lower Lodgepole Formation in the Williston Basin, ND, can be grouped into twelve facies: these facies are graded argillaceous mudstone (F1), massive siliciclastic-argillaceous mudstone (F2a), massive calcareous-argillaceous mudstone (F2b), bioturbated pyrtitized bioclast-bearing mudstone (F3), lenticular mudstone (F4), bioclast-rich wavy mudstone (F5), siliciclastic siltstone (F6), glauconitic siltstone (F7), calcareous siltstone (F8), massive to bioturbated carbonate mudstone (F9), nodular skeletal wackestone (F10), and laminated skeletal packstone (F11). These facies are here presented in order of increasing grain size, carbonate content, and bioturbation from F1 to F11. They are arranged in three fining- and coarsening-upward units that can be identified throughout the basin within the succession. These twelve facies are interpreted to represent distinct processes on a low-inclined shelf system with carbonate occupying the proximal, and siliciclastic mudstones the distal portions of this transect. An overall decrease in energy is reflected from the proximal carbonate to distal siliciclastic facies in this sedimentary system. Nevertheless, most of the mudstone facies still reflect high energy processes operating within the distal portions of the basin; in fact, only one mudstone facies is interpreted to reflect suspension settling under tranquil conditions. Therefore, this study suggests that storm wave base is best placed within the distal siliciclastic mudstones instead of in the proximal carbonates. Carbonate mudstones, deposited above storm wave base but lacking tempestite deposition are therefore interpreted as having been subject to intense degradation of storm-derived bioclasts. A decrease in oxygen concentration is inferred from proximal carbonates to distal siliciclastics as indicated by the decrease in size and type of burrows; yet, the presence of burrows within the most distal facies belt indicates that at least dysoxic conditions prevailed throughout the Williston Basin during the deposition of the 'False Bakken'. Three transgressions and regressions are identified within this succession based on laterally correlated facies patterns and indicate an overall increase in sea level from the beginning to the end of 'False Bakken' times. Sediment starvation occurred in the northeastern and/or southwestern portions of the basin as indicated by the presence of glauconitic siltstones and/or lenticular mudstones at various locations within the succession. However, a source of sediment input is interpreted to be located in the northwestern part of the basin based on a high abundance of detrital silt. In addition, a shift in the basin depocenter southwards from Bakken to lower Lodgepole times is reflected in this succession most likely mirroring an increase in subsidence south of Mountrail County during 'False Bakken' deposition.Item Open Access Field, fluid inclusion and isotope chemistry evidence of fluids circulating around the Harrison Pass pluton during intrusion: a fluid model for Carlin-type deposits(Colorado State University. Libraries, 2012) Musekamp, Charles Oliver Justin, author; Ridley, John, advisor; Sutton, Sally, committee member; Myrick, Christopher, committee memberThe ~60 km, northwest, southeast striking Carlin trend of Northeastern Nevada is host to approximately 40 Carlin-type gold deposits including a number of world class gold deposits. The ~36 Ma Harrison Pass pluton, located in the Ruby Mountains East Humboldt Range in Northeastern Nevada was emplaced along the Carlin trend during back arc-style magmatism between 40 and 32.4 Ma. This timing of plutonic magmatism was also contemporaneous with the regional hydrothermal event responsible for the ~42 to 33 Ma Carlin-type gold mineralization, but an acceptable explanation for the origin and source of fluids responsible for transporting gold remains outstanding. Through a multi-component field and geochemical study of the Harrison Pass pluton, magmatic-meteoric fluid mixing, after Muntean et al. (2011), is supported to explain the composition and origin of fluids responsible for deposition of gold in Carlin-type gold deposits along the Carlin trend. Using fluid inclusion and ō18O and ō13C data combined with field relationships and petrology, a fluid history detailing fluid activity before intrusion, during intrusion (Early Stage) and after intrusion (Late Stage) was constructed. Before intrusion, calcite veins within distal unaltered sedimentary siliciclastic and carbonate rocks were formed from connate waters. Fluids within these veins and wall rocks display typical ō18O (~27 per mil) and ō13C (~2.5 per mil) values of unaltered limestones. Type I (H2O-NaCl-KCl), primary inclusions suggest that fluids are low salinity (~1% Mass% eq. NaCl) and were trapped at low temperatures (Tt~195-340°C). During intrusion and cooling of the Harrison Pass pluton, primitive, hot magmatic volatile phases were expelled and are interpreted to be responsible for the formation of miarolitic cavities, skarn, phyllic, and potassic alteration of wall rocks, and many quartz and calcite veins proximal to the pluton contact. Evidence for magmatically derived fluids around the pluton is provided by high homogenization temperatures of Type III (H2O-CO2-NaCl-KCl), CO2-rich inclusions in miarolitic cavities, and vapor-rich Type II (H2O-NaCl-KCl) inclusions in hydrogrossular and quartz within skarn wall rocks and quartz veins. Further corroboration is provided by near magmatic ō18O and ō13C values (~13 and -0.25 per mil) of skarn wall rocks and calcite-polymetallic sulfide veins. A later, cooler convecting meteoric phase (Late Stage) driven by the heat during and after intrusion is observed within thick, fault hosted, steeply dipping quartz veins and vugs crosscutting the Harrison Pass pluton and in skarn wall rocks. It is interpreted, after Muntean et al. (2011), that Type II vapor-rich, primary inclusions found within Early Stage quartz veins, miarolitic cavities, and skarn wall rocks represent the vapor-rich magmatic phase in which Au and other base metals were transported. As the vapor-rich fluid rose through the crust, it would have evolved and cooled and may be represented by the less vapor-rich, Early Stage, Type I inclusions within phyllically altered wall rocks and calcite-polymetallic sulfide veins. Further cooling and ascent of this fluid would have interacted with convecting meteoric waters at shallower depths. At this level, all fluids would have undergone some mixing, which is broadly supported by the wide range of recalculated ō18O values in this study. As the magmatic phase becomes more diluted by circulating meteoric convection (Late Stage), low salinity (~3% Mass% eq. NaCl) and low temperature (Tt~200 to 480°C) secondary inclusions in skarn altered wall rocks in close proximity to the contact and major fault-hosted quartz veins/vugs crosscutting the Harrison Pass pluton are trapped. Infiltration of meteoric fluids around the contact is supported by mixed meteoric-connate ō18O and ō13C signatures in skarn wall rocks and calcite veins. It is speculated that mixed magmatic-meteoric fluids were then transported and focused along high angle faults along the flanks of the Harrison Pass pluton where a mixture of further cooling, oxidation and fluid-rock reactions resulted in gold deposition with pyrite and arsenopyrite within sedimentary country rocks along the Carlin trend.Item Open Access Fluorinated materials synthesis and characterization for energy storage and energy conversion applications(Colorado State University. Libraries, 2015) Bukovsky, Eric V., author; Strauss, Steven H., advisor; Ackerson, Christopher, committee member; Crans, Debbie, committee member; Barisas, B. George, committee member; Sutton, Sally, committee memberThe synthesis and characterization of multiple fluorinated, p-block, cage, and organic compounds will be presented. The research effort is split up in to main topics, (i) fluorinated superweak anions based on B12 cages, and (ii) perfluoroalkylation of polycyclic aromatic hydrocarbon (PAH) and fullerene compounds. In the first three chapters, superweak anion research is presented; a new purification method for the synthetic intermediate K2B12F12, synthesis and thermal and physical characterization of highly purified (H3O)2B12F12·nH2O, Li2B12F12 and Na2B12F12 (synthesized from K2B12F12), and an HF-free, improved synthesis method and characterization of KB12F11NH3. Furthermore, the unanticipated, rapid fluorination of KB12H11NH3 in the presence of HF, contrary to, previously observed, slowed fluorination of K2B12H12 in the presence of HF, will also be described. Single crystal X-ray structures of three new isomers of C60(CF3)10 are discussed, and one putative isomer of C60(CF3)10 is confirmed along with comparisons of their crystal packing properties compared to 1,9-C60(cyclo-CF2(2-C6F4)), and industry-standard fullerene acceptor phenyl-C61-butyric acid methyl ester (PCBM). Discussion of how the structural and electrochemical data of the new C60(CF3)10 isomers and 1,9-C60(cyclo-CF2(2-C6F4)) agree with currently accepted literature will also be discussed. A new metal reactor design for the radical reactions of CF3I and polycyclic aromatic hydrocarbons (PAH) and fullerenes, and initial results will be discussed and compared to previous reaction methods. Single crystal X-ray structures of four separate compounds believed to be "trapped intermediates" formed from the radical substitution reaction isolated from radical reactions with CF3I using different PAHs and different reactions conditions will be discussed as well as the implications these trapped intermediates have on the proposed mechanism of CF3• radical substitution reactions. Crystal packing and nearest molecule analysis of five PAH(CF3)n will be compared to a single crystal X-ray structure of triphenylene with a C4F4 substitution. Insights into the structural effects of CF3 substitutions compared to the flat C4F4 substitutions, and, how those effects would translate into electronic communication in the solid state will be discussed. Finally, wet milling of metallurgical grade silicon in an attritor mill, under anaerobic and aerobic conditions with and without surface passivating additives to study the affects oxygen and additives can have on milled particle properties such as, crystallinity by powder X-ray diffraction, surface bonds by X-ray photoelectronspectroscopy, dynamic light scattering particle size, N2 gas uptake BET surface area and reactivity towards oxygen will be discussed. Under anaerobic conditions silicon was found to form Si–C bonds in the presence of dry- air-free heptane. Additionally, the extensive effect oxygen has on the comminution of silicon and the surprising result that, even in aerobic conditions, formation of Si–C bonds is observed. All of the research described in this dissertation has applications in one or multiple energy storage or energy conversion devices. The superweak anion salts as electrolyte salts in battery or fuel cell, C60(CF3)10 and 1,9-C60(cyclo-CF2(2-C6F4)), as electron acceptor materials in organic photovoltaic devices, and multiple PAH(CF3)n compounds as OLED active layer materials.Item Open Access Hydraulic and chemical properties of geosynthetic clay liners in mining applications(Colorado State University. Libraries, 2017) Conzelmann, Joel, author; Scalia, Joseph, advisor; Shackelford, Charles, committee member; Sutton, Sally, committee memberGeosynthetic clay liners (GCLs) are thin (< 10 mm) factory manufactured hydraulic barriers used in environmental containment systems because of the propensity of bentonite to swell and immobilize water which results in low hydraulic conductivity, k (≤ 2-3×10-11 m/s). GCLs consist of bentonite (clay) bonded or sandwiched between layer(s) of geotextile and/or geomembrane. The effectiveness of GCLs in containment applications has been demonstrated for systems with low ionic strength solutions and leachates, such as municipal solid waste leachates. Increasingly, GCLs are being used in mining applications; these applications require further research and laboratory testing to demonstrate barrier effectiveness. Existing standard test methods are not well suited for testing of mine-waste-leachates; simple procedures to collect effluent for analysis are lacking, commercially available testing equipment is typically incompatible with extreme pH solutions often encountered, and the use of backpressure is recommended requiring testing at elevated pressures. To overcome these limitations, an alternative gravity method without backpressure, paired with a permeameter constructed from non-reactive materials and intended to minimize clogging was used. Validation of the gravity method is demonstrated through k and hydration testing with synthetic mine waste leachates and comparative tests performed by a standard method. Tests results support that GCLs attain saturation, and that the gravity method does not exhibit uncharacteristically low k due to unsaturated conditions. However, the gravity method revealed the possibility of preferential flow through fiber bundles for GCLs with higher degrees of needle punching which was not observed in standard method tests. The cause of the discrepancy between the two methods is hypothesized to be associated with applying backpressure in the standard method, indicating that the standard method may provide an un-conservative estimate of k for higher peel strength GCLs. Regardless, bentonite saturation is shown to occur without backpressure under conditions typical of k testing, illustrating that saturated (maximum k) tests can be achieved without backpressure. The k of GCLs to synthetic mine leachate solutions was tested using the gravity method with the chemical-resistant permeameter. Three different mine waste leachates are investigated, a neutral pH synthetic gold mining process solution, a high pH synthetic bauxite mining process solution, and a low pH synthetic copper mining process solution. Three different GCL products were also investigated, two higher peel strength GCLs (2170 N/m and 3500 N/m), and a standard peel strength GCL (700 N/m). The preliminary results of k testing are reported.Item Open Access Identification and validation of screening methods for assessment of the sheening potential of embedded oil in sediments(Colorado State University. Libraries, 2020) Sitler, Katherine, author; Scalia, Joe, advisor; Sale, Tom, advisor; Sutton, Sally, committee memberSediments impacted with petroleum hydrocarbons (oil) may sheen due to ebullition-driven transport or sediment disturbance. The goal of this project was to develop a screening method that can be deployed on a small autonomous watercraft that will provide a reliable indication of sheening potential of embedded oil in shallow sediments. Different potential probes and methods were explored to penetrate sediments and determine sheening potential. Preliminary probe identification focused on development of a standardized laboratory column to test different probes and penetration methods to determine which probe has the highest probability to generate a sheen. Column tests were performed that consisted of different combinations of five crude oil types and a control (no oil embedded), seven probe candidates, two types of oil deposits, two targeted sheen levels, and with or without embedded air. Based on the data collected, a direct push rod with water injection had the greatest potential to generate a sheen.Item Open Access Petrology and geochemistry of alteration types within a multiphase system and implications for the presence of a porphyry root, Harrison Pass Pluton, Nevada(Colorado State University. Libraries, 2017) Racosky, Alexandra, author; Ridley, John, advisor; Sutton, Sally, committee member; Bareither, Christopher, committee memberTo view the abstract, please see the full text of the document.Item Open Access Predictions of produced water quality and quantity for spatially-distributed wells in Niobrara formation(Colorado State University. Libraries, 2012) Mingazetdinov, Ildus F., author; Carlson, Kenneth, advisor; Sutton, Sally, committee member; Catton, Kimberly, committee memberTwo main problems facing the oil and gas industry are the availability of water for well construction and disposal of the produced water. Produced water is typically only treated for a limited number of constituents, and common disposal options have been deep well injection, evaporation or discharge to wastewater treatment plants. However, because of factors such as regulations, local water shortage, and bans on disposal via deep well injection, the future will require much of the produced water be treated and eventually recycled and reused for future field development or other beneficial uses. Multiple cost effective produced water treatment methods have been developed but limited research has been done to understand produced water production volumes and quality from oil and gas fields. Accurate predictions of produced water volumes and quality over a period of time can be used to optimize design and siting of water handling and treatment facilities in a spatially heterogeneous shale oil and gas field. The information can also be used to model availability of water resources and plan long term recycling strategies for augmenting regional surface water supplies. This study describes protocols to estimate and predict produced water quantity and quality from shale gas wells and applies these to a case study of Noble Energy Inc. wells in Yuma County, CO. Three different protocols of water production prediction were developed based on temporal and spatial variations of water quantity. Dissolution kinetics and geospatial data were used to develop a water quality prediction framework. A Microsoft Excel based tool, which uses a combination of water quantity and quality protocols, was developed to predict water production and total dissolved solids (TDS) from Noble Energy Inc. wells in Yuma County for different field development scenarios. A framework for interactive web based applications based on developed protocols is also provided. This study also provides a framework for development of GIS based web applications, which can provide an analysis platform for producers and consulting firms to predict water production and/or water quality, optimize location of treatment facilities, truck routings and help make other decisions related to water management. The study showed that using decline models to predict water production from shale gas fields will provide better long term predictions rather than using historical production average values. The case study and scenarios used for Noble Energy wells in Yuma County demonstrate that these prediction methods can be used in any other shale gas field by altering decline models and coefficients.Item Open Access Processes governing the performance of oleophilic bio-barriers (OBBs) – laboratory and field studies(Colorado State University. Libraries, 2018) Tochko, Laura, author; Sale, Tom, advisor; Scalia, Joe, committee member; Sutton, Sally, committee memberPetroleum sheens, a potential Clean Water Act violation, can occur at petroleum refining, distribution, and storage facilities located near surface water. In general, sheen remedies can be prone to failure due to the complex processes controlling the flow of light non-aqueous phase liquid (LNAPL) at groundwater/surface water interfaces (GSIs). Even a small gap in a barrier designed to resist the movement of LNAPL can result in a sheen of large areal extent. The cost of sheen remedies, exacerbated by failure, has led to research into processes governing sheens and development of the oleophilic bio-barrier (OBB). OBBs involve 1) an oleophilic (oil-loving) plastic geocomposite which intercepts and retains LNAPL and 2) cyclic delivery of oxygen and nutrients via tidally driven water level fluctuations. The OBB retains LNAPL that escapes the natural attenuation system through oleophilic retention and enhances the natural biodegradation capacity such that LNAPL is retained or degraded instead of discharging to form a sheen. Sand tank experiments were conducted to visualize the movement of LNAPL as a wetting and non-wetting fluid in a water-saturated tank. The goal was to demonstrate 1) the flow of LNAPL as a non-wetting fluid in sand, 2) the imbibition of LNAPL as a wetting fluid on the geocomposite, and 3) the breakthrough of LNAPL after saturating the geocomposite to the point of failure (sheens in the surface water). Dyed diesel was pumped through a tank with sand and geocomposite and photographed to document movement. Diesel was the non-wetting fluid in the sand and moved in a dendritic pattern. Diesel was the wetting fluid on the geocomposite and uniformly imbibed horizontally across the geocomposite before breakthrough to the overlying sand layer. A second set of laboratory experiments was designed to estimate the aerobic and anaerobic OBB degradation rates of LNAPL in field-inoculated sediment. Unfortunately, due to a flaw in the experimental design, the mass balance could not be completed, and degradation rates were not calculated. The setup was designed to emulate field conditions as best practically possible and to observe the effects of water table fluctuations, different loading rates, and iron. The effluent pumping system designed to remove water in the water fluctuation columns also inadvertently removed LNAPL, creating a mass balance discrepancy for the aerobic columns. Though degradation rates could not be calculated from this experiment, the experiment did visually document the changing redox conditions in the columns, such as formation of a black precipitant (likely iron sulfides) around LNAPL. Ideally, the limitations of this experimental design can be addressed for future research to eventually resolve degradation rates for OBBs. The success of a 3.8 m by 9.3 m demonstration OBB at a field site on a tidal freshwater river resulted in replacing the demonstration OBB with a 3.8 m by 58 m full-scale OBB. The construction event provided a unique opportunity to sample the demonstration OBB after a four-year deployment. The sampling results advanced the mechanistic understanding of how OBBs work to reduce LNAPL releases at GSIs. Sampling revealed the material was suitable for field LNAPL loading rates and was not compromised by field conditions such as ice scour or sediment intrusion. LNAPL analysis showed no LNAPL on the geocomposite or in the underlying upper sediment (0-10 cm). Diesel range organic (DRO) concentrations in the low 1,000s of mg/kg were observed in the sediment 10-20 cm below the geocomposite. LNAPL composition analysis suggests that the majority of the compounds are polar in the lower sediments (10-20 cm), providing a line of evidence that petroleum liquids have been oxygenated. Microbial data show the average number of bacterial 16s transcripts in the geocomposite is larger than in the sediment layers, confirming that the geocomposite is suitable substrate for microbe growth. The observation of ferric iron suggests that ferric/ferrous iron cycling may play a role in degradation processes, where the ferric iron acts as a "bank" of solid-phase electron acceptors. This sampling event suggests that LNAPL biodegradation rates in and below the OBB are comparable to the LNAPL loading rates.Item Open Access Soil carbon saturation: a new model of soil organic matter stabilization and turnover(Colorado State University. Libraries, 2006) Stewart, Catherine E., author; Paustian, Keith H., advisor; Six, Johan, committee member; Conant, Richard T., committee member; Sutton, Sally, committee memberThe soil C saturation concept suggests an ultimate capacity of the soil to store C, dictating the rate and duration that soil may be effective in mitigating increasing atmospheric C02. This places a physicochemical limit on soil that is associated with textural, mineralogical and structural soil properties. This concept has been articulated in terms of four theoretical pools capable of C saturation: non-protected, physically- (micro-aggregate), chemically- (silt + clay), and biochemically-protected pools. My dissertation represents a multifaceted approach to examine C saturation in both whole soil and measurable soil fractions representing the four conceptual C pools. I evaluate the soil C saturation concept theoretically by modeling these relationships using published whole soil data, primary field data and through laboratory experiments. Analyses using published long-term soil C data from agroecosystem experiments suggested that within a given site, there was little support for models including C saturation, but when all sites were combined; there was strong support for the C saturation model. In general, published data were too sparse to adequately test individual sites. To evaluate the concept of C saturation for the four C pools, I used a three-part density, chemical, and physical fractionation scheme combined with modeling, using new data collected from eight agroecosystems in the US and Canada. I found that the chemically- and biochemically-protected pools showed strong evidence for C saturation, while the non-protected and physically-protected pools were non-saturating. In a 2.5 year laboratory experiment, I tested C stabilization rates and limits at two C addition rate to soils differing in soil C content and physicochemical characteristics. I found C saturation dynamics were most evident in the chemically-, biochemically- and some micro-aggregate protected C pools. I found greater C accumulation in the non-protected pool of the high C soil, suggesting C saturation of other pools. I conclude that SOC sequestration in many soils may be influenced by C saturation dynamics, impacting both decomposition kinetics and C stabilization. Soil C sequestration may be overestimated in models that do not account for C saturation dynamics.Item Open Access Structural analysis along the Ouray fault, southwestern Colorado: implications for the kinematic development of the late Paleozoic Ancestral Rocky Mountains(Colorado State University. Libraries, 2021) Johnson, Erinn P., author; Singleton, John, advisor; Sutton, Sally, committee member; Sharp, Julia, committee memberThe Ouray fault in southwest Colorado provides insight into the geometry and kinematics of deformation during the formation of the late Paleozoic Ancestral Rocky Mountains (ARM). The Ouray fault strikes WNW-ESE and dips subvertically to steeply south, juxtaposing the Paleoproterozoic Uncompahgre Group on the south side against Mississippian-Pennsylvanian strata on the north side. Kinematic data from the Ouray fault, adjacent small-scale faults, the observed offset, and folds in Paleozoic strata indicate that the Ouray fault records sinistral transpression. Using the average 15° W-plunging slickenlines from the principal slip plane, we estimate the total oblique sinistral displacement of the fault to be ~600 to 800 m. The uniformly overlapping Mesozoic strata atop the projected trace of the Ouray fault indicate that the fault is a preserved ARM structure not reactivated during the Laramide orogeny. The Ouray fault is oriented subparallel to the Uncompahgre Group bedding and follows the weaker Uncompahgre phyllite for most of its length, suggesting the preexisting structures within the Uncompahgre Group greatly influenced the orientation of the Ouray fault. N-S- to NW-SE-striking joints and quartz veins in all geologic units spanning the Paleoproterozoic to the Cenozoic postdate slip on the Ouray fault and likely formed during Cenozoic magmatism. A sample of calcite from the principal slip plane of the Ouray fault yielded a U-Pb date of 39.3 ± 6.2 Ma. I interpret this date to record resetting by late Eocene hydrothermal fluid flow. The record of strain around the Ouray fault may be representative of the southwestern margin of the Ancestral Uncompahgre uplift in Colorado. This study supports recent tectonic models for the ARM system which propose that ARM uplift was driven by NE-SW compression during the Pennsylvanian and Permian periods.Item Open Access The magmatic-hydrothermal fluid history of the Harrison Pass Pluton, Ruby Mountains, NV: implications for the Ruby Mountains-East Humboldt Range metamorphic core complex and Carlin-type Au deposits(Colorado State University. Libraries, 2016) Gates, Christopher Harry, author; Ridley, John, advisor; Sutton, Sally, committee member; Strauss, Steven, committee memberIntrusion of the ~36 Ma, calc-alkaline, granodiorite-monzogranite Harrison Pass Pluton (HPP) occurred as magmatic fronts migrated southwest across the Great Basin during the Eocene. The HPP was locally intruded into the Ruby Mountains-East Humboldt Range (RMEHR), a classic Cordilleran metamorphic core complex that would undergo rapid tectonic exhumation during the late Cenozoic. Although the emplacement depth of the HPP provides an estimate for the magnitude and timing of subsequent uplift, disagreement exists between published mineral thermobarometry data and stratigraphic reconstructions. Synchronous with emplacement of the HPP was a regional hydrothermal fluid event responsible for deposition of >200 Moz of Au in sediment-hosted Carlin-type deposits (CTD's) along four linear trends. Magmatic, meteoric, and metamorphic models have been invoked to explain the origin of fluids and Au for CTD's, but few studies have directly examined the fluids generated by a potential source intrusion such as the HPP. Investigation of the magmatic-hydrothermal fluid history of the HPP, particularly the pressure-temperature conditions of fluid entrapment and fluid geochemistry, is an effective means of testing and improving existing models for the development of the RMEHR metamorphic core complex and for the origin of CTD's. Field and petrographic observations of pegmatites, aplites, miarolitic cavities, quartz veins, and multiple types of hydrothermal alteration, coupled with data from fluid inclusion microthermometry, LA-ICP-MS fluid inclusion geochemistry, and oxygen stable isotopes from magmatic and hydrothermal quartz, demonstrate that two-stage intrusive assembly was paralleled by a two-stage magmatic-hydrothermal fluid system. Early stage fluid activity was dominated by two aqueous, low salinity (~3 wt % eq. NaCl), B-Na-K-Rb- Sr-Cs-bearing, ore metal-poor fluids. These fluids were entrapped at ~600-700°C and ~2400-7600 bar in pegmatites, miarolitic cavities, and quartz veins within early stage units, as well as in quartz and calcite veins in base-metal skarns along the pluton margin and in the contact metamorphic aureole. Late stage fluid activity was dominated by one aquo-carbonic, low salinity (~3 wt % eq. NaCl), B-Na-K-Rb-Sr-Cs-bearing, ore metal-poor fluid. This fluid was entrapped at 570-680°C and ~4800-7200 bar in pegmatites, aplites, and quartz veins, and did not migrate out of late-stage intrusive units. Magmatic δ18O values for quartz demonstrate that this magmatic-hydrothermal fluid system evolved without significant dilution from meteoric inputs until the late influx of post-intrusion hydrothermal fluids, interpreted to be of mixed magmatic-meteoric origin. These fluids were aqueous, low-temperature (320-410°C), low salinity (<4 wt % eq. NaCl), and were entrapped at <2400 bar in fault-hosted microcrystalline quartz veins.The entrapment conditions for early stage magmatic-hydrothermal fluids determined from fluid inclusion microthermometry data indicate that the HPP was emplaced at depths of 9-18 km in the Ruby Mountains-East Humboldt Range. Brittle-ductile deformation of the HPP on the regionally-exposed Ruby Mountain Shear Zone indicate that at least 9 km of vertical exhumation has occurred since the intrusion of the HPP. Such emplacement depth estimates are consistent with published mineral thermobarometry from the HPP and from nearby metamorphic rocks. It is interpreted that the disparity between these estimates and the relatively shallow minimum emplacement depths of 4-6 km suggested by stratigraphic reconstructions is supportive of the existence of poorly preserved, Mesozoic thrust sheets that augmented the thickness of the overlying rock package during the Eocene. Although a well-accepted model for the origin of fluids and Au for CTD's remains outstanding, the model of Muntean et al. (2011) argues for the separation of a low-salinity, vapor-rich, Au-partitioning fluid from a high-salinity, base metal-partitioning fluid in mid- crustal magma chambers as a critical process in the evolution of CTD ore fluids. Although HPP emplacement depths and the existence of a robust magmatic-hydrothermal fluid system are broadly supportive of this model, no evidence of a high-salinity fluid was observed. Low concentrations of base metals (Cu, Pb) and CTD pathfinder elements (As, Tl) relative to whole-rock values are not consistent with the efficient fluid partitioning of metals invoked by Muntean et al. (2011). Also, low concentrations of CTD pathfinder elements relative to published values for CTD ore fluids indicate that the HPP was not Au-enriched. However, similar salinities and δ18O values suggest that HPP fluids may represent the minor magmatic component of ore fluids detected at some CTD's, but other fluid inputs and an external Au source would be required to produce these ore fluids. Thus, it is suggested that the magmatic-hydrothermal fluid history of the HPP is more consistent with a dominantly amagmatic fluid model for the origin of CTD's.Item Open Access Variation in clinopyroxene texture, composition, and crystallization depth of Late Cretaceous to Early Eocene lamprophyric rocks from alkaline calc-alkaline magmatic complexes of Montana, USA(Colorado State University. Libraries, 2022) McCane, Jacob, author; Ridley, John, advisor; Bareither, Christoper, committee member; Scarberry, Kaleb, committee member; Sutton, Sally, committee memberLamprophyres are spatially and temporally associated with many types of hydrothermal ore deposits and have been argued to be a marker in mineral exploration. A reconnaissance study of lamprophyric rocks in central Montana, namely the Central Montana Alkalic Province (CMAP) is presented that details the variations of petrographic textures and clinopyroxene (Cpx) mineral chemistry from different Late Cretaceous to Early Tertiary aged alkalic to calc-alkaline magmatic complexes. Using current International Union of Geological Sciences (IUGS) standards, lamprophyric rocks studied from the Late Cretaceous Bull Mountain/Golden Sunlight mining operations are found to be predominately minette > vogesite > kersantite varieties of lamprophyres. The Highwood Mountains lamprophyric rocks of Eocene age are classified as vogesites > sannaites > minnettes ≈ spessartites. Crazy Mountain (Crazies) lamprophyric rocks of Eocene age are monchiquites > vogesites > kersantites > spessartites. The sapphire-bearing Yogo dyke lamprophyre of Eocene age is classified as an ouachitite. Lamprophyric rocks occur as dykes and display porphyritic and panidiomorphic textures with dominant macrocrysts of Cpx, biotite, with lesser olivine and hornblende that range in size from a few centimeters in length to microcrystalline (<10 µm) matrix constituents. Leucocratic circular ocelli structures as well as bent and strained crystals of biotite are present within all lamprophyric rocks from the CMAP. Extreme heterogeneity exists within lamprophyres ranging from macroscale dyke swarm features to microscale Cpx macrocrysts assemblages captured in a single thin section. Cpx from every region of the CMAP display intricate optical zonations associated with complex compositional variations across core to rim analytical traverses and display disequilibrium features like spongy textured melt pockets. Within the CMAP the Cpx classify as diopside, Fe-rich diopside, Ca-rich diopside or augite and do not contain uniform textures or zonations. Cpx of the Crazies are strictly diopsides and the only region with augite is Bull Mountain/Golden Sunlight. Cpx macrocrysts from each region of this study are separated into Types based off of differing textural features from back scatter electron imaging and under the petrographic microscope. All Types across the CMAP are predominately normally zoned and are interpreted as antecrysts or xenocrysts that host compositions and textures that record disequilibrium with the host magma during crystallization. B Types of Bull Mountain/Golden Sunlight are enriched in Cr2O3 and FeO. H Types from the Highwoods are similar to B Types but record Step-zoning characteristics and contain the greatest proportion of both normal and reverse zoning characteristics. C Types of the Crazies record lower values of TiO2, Al2O3, CaO, and Fe2+ /Fe3+ ratios but have higher Na2O levels than all other Types of the CMAP. Y Types of the Yogo Dyke host the most ultramafic signatures with elevated Mg#, TiO2, Al2O3, Cr2O3, and CaO levels along with the lowest SiO2 and FeO composition of all Types of the CMAP. Barometric estimates of the pressure of crystallization for Cpx are presented from the CMAP, mean crystallization estimates are as follows: Bull Mountain/Golden Sunlight = 15.1 ± 1.5 kbar (56 km), Highwood Mountains = 11.4 ± 1.5 kbar (42 km), Crazy Mountains = 7.1 ± 1.5 kbar (26 km), Yogo Dyke = 14.3 ± 1.5 kbar (53 km). Cpx macrocrysts crystalized near the lower crust-mantle boundary and barometry from Bull Mountain/Golden Sunlight likely records a deeper magma reservoir and plumbing system than previously thought for the Boulder Batholith. Lamprophyric rock petrogenesis cannot be explained by simple fractionation processes because the antecrysts do not follow regular fractionation trendlines. Multiple complex open system magmatic processes are likely at play when controlling lamprophyric magma composition. Drastically different compositional variations of C Types compared to others of the CMAP confirm that the parent magma of lamprophyric rocks originating from the Crazies is significantly different than other areas of this study. Primary melts from the Crazies and the Highwoods likely had an enriched composition and heavy metasomatic influence. Evidence for multiple recharge and mixing events exists within all lamprophyric rocks of the CMAP. Hybridization of mafic and felsic magmas likely influenced the petrogenesis of lamprophyric rocks from Bull Mountain/Golden Sunlight, the Highwood Mountains, the Crazy Mountains, and the Yogo Dyke.