Geology topics

Bonnie McDevitt

Publications and source records attributed to Bonnie McDevitt.

15 recordsLinked to original sources

USGS2026

Elemental and isotope geochemistry of Smackover Formation brines in Alabama and Arkansas: Implications for fluid mixing and water-rock interaction

This study investigates the geochemical characteristics of brines within the Upper Jurassic Smackover Formation in Alabama and Arkansas through elemental and isotopic analyses and geochemical modeling to reveal the extent and nature of fluid mixing and water-rock interactions. Smackover Formation brines exhibit Na-Cl-Ca hydrogeochemical facies and sulfate depletion relative to seawater. Lower sulfate concentrations, coupled with high H 2 S concentrations in some brines (0-364 mg/L) at temperatures >80°C, suggest that thermochemical sulfate reduction occurred. Cl/Br and Na/Br ratios indicate that salinity was controlled by the mixing of meteoric water with evaporated seawater that had reached halite saturation, rather than by halite dissolution. The δ 18 O and δ 2 H values of the brines also suggest mixing between meteoric water and evaporated seawater that had reached gypsum and halite saturation. Geochemical modeling of seawater evaporation predicts a Cl-Na or Cl-Mg facies after halite saturation, contrasting with the observed Cl-Ca dominance of the Smackover Formation brines. The Ca-enriched brines may have evolved from Cl-Mg-dominated evaporated seawater through dolomitization of limestone. The 87 Sr/ 86 Sr ratios range from 0.70740 to 0.71048, higher than the average of Jurassic seawater (0.707). The non-linear relationship between 87 Sr/ 86 Sr and 1000/Sr suggests alteration of brine geochemistry by fluid mixing or by inputs from Sr and 87 Sr-enriched rock sources. Lithium concentrations are positively correlated with 87 Sr/ 86 Sr ratios and TDS in brines enriched in these constituents. These correlations suggest deeper-seated geogenic sources and have implications for Li exploration in the northern Gulf Coast basin. Normal faults associated with the pre-Jurassic topography may have provided potential pathways for brine migration into the Smackover Formation under the influence of overpressure or thermohaline convection in the Gulf Coast.

Alabama↗

USGS2026

Per- and polyfluoroalkyl substances in waters associated with oil and gas development in the Denver Basin

Use of per- and polyfluoroalkyl substances (PFAS) in the petroleum industry could be a cause for concern due to the large volumes of produced water (PW) generated during oil and gas extraction, the reuse of these wastes in water-stressed regions, and adverse health outcomes related to PFAS exposures. However, PW PFAS characterization is nearly absent in the literature, and hydraulic fracturing (HF) chemical disclosures often omit the identities of additives as proprietary. Here we evaluate PFAS in PW samples from three petroleum wells in the Denver Basin during their first year of production. Total concentrations of targeted PFAS (Σ 40 PFAS) were < 35 ng/L in PW samples, with short-chain PFAS like perfluorobutanoic acid persisting throughout the sampled duration. Analysis of freshwater inputs for hydraulic fracturing (Σ 40 PFAS ~ 113 ng/L) and mixed fracture fluid (Σ 40 PFAS ~ 69 ng/L) indicated much of the targeted PFAS content was derived from the input water, and not from HF additives, however samples subjected to oxidation indicated the presence of PFAS precursors that would not be detected by targeted analysis. This study highlights that while PFAS content is low in the studied PWs, the potential for redistribution of PFAS in the environment may be a consideration for reuse applications.

Colorado, Nebraska, Wyoming↗

USGS2026

Evaluating machine learning approaches to identify and predict oil and gas produced water lithium concentrations

Recently, the demand for battery-grade lithium has substantially increased, largely due to electrification of the transportation sector. The search for new lithium sources has turned to produced waters (frequently brines), a large-volume wastewater by-product of oil and gas extraction. Geochemical analysis indicates the presence of varying concentrations of lithium from produced water samples collected across the United States and represented in the U.S. Geological Survey’s National Produced Water Geochemical Database, as well as mixtures of Marcellus Shale produced water included in the Pennsylvania Department of Environmental Protection’s Oil and Gas Well Waste Reports. We first examined whether the geochemical signature of the lithium-bearing produced waters is sufficiently distinct so that machine learning (ML) can be used to correctly classify samples to the formation of origin. The produced water sample data used to assess classification accuracy were from the Marcellus Shale, Utica Shale and Point Pleasant Formation (Utica), and Smackover Formation oil and gas wells. Further, we evaluated the potential for ML to accurately classify Marcellus Shale produced water spatially (i.e., northeast versus southwest Pennsylvania). We then investigated whether ML algorithms applied to a suite of geochemical concentration data (i.e. Ba, Br, Cl, K, Mg, Sr) may be used to predict the lithium concentration of an unknown sample. Finally, we applied an estimated economic lithium grade cutoff of 150 milligrams per liter (mg/l) and assessed the utility of ML to predict whether a produced water sample would fall above or below the grade cutoff based on the suite of geochemical parameters. Four machine learning algorithms—Random Forest (RF), Gradient Boosting Trees (GBT), Extreme Boosting (XGBoost), and Deep Neural Networks (DNN) were assessed. This study successfully demonstrates that all four machine learning methods can precisely and accurately estimate lithium concentrations and geologic formation classification. The products of this study contribute to the growing body of knowledge aimed at expanding the lithium resource base within the United States.

Alabama, Arkansas, Florida, Georgia, Louisiana, Mi↗

USGS2026

Lithium brine potential of North Dakota: Results from the 2025 sampling program

Lithium (Li), classified as a critical mineral and key in energy storage applications because of its high energy density, faces unprecedented demand. This has driven interest in unconventional sources of Li, especially brines from sedimentary basins. Accordingly, the spatial distribution of basinal brinehosted Li resources across North America is becoming better defined, including the Williston Basin underlying Saskatchewan, Canada. This has led to growing investment and exploration by industry throughout the 2020s; however, despite this interest, the Li potential of basinal brines of the Williston Basin in North Dakota remain underexplored. This work presents the results from the 2025 joint brine sampling campaign between the North Dakota Geological Survey, the United States Geological Survey (USGS), and The University of Texas at Austin. Twenty-seven fluid samples were collected from producing oil and water source wells from eight stratigraphic intervals across western North Dakota and analyzed for major cation and anion concentrations. Similar to southeastern Saskatchewan, the highest Li concentrations were identified in the Devonian Duperow Formation, with concentrations up to 179 mg/L being observed in a well commingled between the Duperow and Red River Formations. Some samples from the overlying Birdbear Formation exceeded 75 mg/L, whereas Li concentrations were lower in the Madison Group (33-44 mg/L) and the Three Forks (50 mg/L), Dawson Bay (43 mg/L), Winnipegosis (23 mg/L), and Red River (40.0 mg/L) Formations. This work indicates Li resource potential exists across the Williston Basin and advances our understanding of the Li distribution in basinal brines which could provide a new domestic source of this critical mineral.

North Dakota↗

USGS2025

Pathways for potential exposure to onshore oil and gas wastewater: What we need to know to protect human health

Produced water is a chemically complex waste stream generated during oil and gas development. Roughly four trillion liters were generated onshore in the United States in 2021 (ALL Consulting, 2022, https://www.gwpc.org/wp-content/uploads/2021/09/2021_Produced_Water_Volumes.pdf ). Efforts are underway to expand historic uses of produced water to offset freshwater needs in water-stressed regions, avoid induced seismic activity associated with its disposal, and extract commodities. Understanding the potential exposures from current and proposed produced water uses and management practices can help to inform health-protective practices. This review summarizes what is known about potential human exposure to produced water from onshore oil and gas development in the United States. We synthesize 236 publications to create a conceptual model of potential human exposure that illustrates the current state of scientific inquiry and knowledge. Exposure to produced water can occur following its release to the environment through spills or leaks during its handling and management. Exposure can also arise from authorized releases, including permitted discharges to surface water, crop irrigation, and road treatment. Knowledge gaps include understanding the variable composition and toxicity of produced water released to the environment, the performance of treatment methods, migration pathways through the environment that can result in human exposure, and the significance of the exposures for human and ecosystem health. Reducing these uncertainties may help in realizing the benefits of produced water use while simultaneously protecting human health.

Environmental Health Perspectives↗

USGS2025

Evaluation of solid bitumen created from marine oil shale bituminite under hydrous and anhydrous pyrolysis conditions

To test the influence of environmental conditions on aromaticity of solid bitumen generated during petroleum generation, four organic-rich (26–36 wt% total organic carbon) oil shale samples collected from the Neoproterozoic–Lower Cambrian restricted marine Salt Range Formation in the upper Indus Basin, Pakistan, were pyrolyzed under hydrous and anhydrous conditions. Experiments used closed system batch reactors at subcritical water temperatures between 300 and 370°C for 72 h. Thermal conversion of bituminite in the Salt Range oil shales created a newly formed solid bitumen, similar to previous observations from experiments on the Eocene lacustrine Green River Formation Mahogany zone oil shale. Newly formed solid bitumen in the Salt Range Formation oil shales generally has higher reflectance (R o ) in hydrous residues compared to anhydrous experiments subjected to the same time-temperature conditions, also similar to prior observations. This finding supports the hypothesis that radical disproportionation is favored in the presence of hydrogen contributed by water, promoting aromatization in the solid bitumen residue with concomitant increased expulsion of saturated hydrocarbons. Indigenous solid bitumen (and vitrinite in a comparison sample) also shows higher reflectance values in hydrous versus anhydrous residues, indicating that additional aromatization in the presence of exogenous hydrogen occurs both in newly formed organic matter and in organic matter that is present throughout the experiment. Despite similarities in their bulk rock geochemical screening parameters, R o evolution shows different trajectories amongst the four Salt Range oil shales, suggesting as-yet undetermined differences in kinetic properties which are probably related to differences in a priori chemical composition. These results have implications for the use of solid bitumen reflectance (BR o ) as a thermal proxy, suggesting BR o values and appearance could vary as a function of the concentration of water. Variation in water concentration may be present at the reservoir or formation scale, but may also be present at a much finer scale in tight oil shales where permeability is several orders of magnitude lower than conventional reservoirs. Therefore, local variations in the presence of water potentially could explain substantial variation in BR o values and appearance in closely spaced source rock samples and even within an individual microscope field.

Journal of Analytical and Applied Pyrolysis↗

USGS2024

Lithium resource in the Smackover Formation brines of Southern Arkansas

Lithium-rich brine deposits occur throughout the United States, including in the Smackover Formation. The concentration of lithium in Smackover Formation brines was predicted across southern Arkansas by using a machine-learning model that incorporated lithium concentration data and geologic information. Between 5.1 and 19.0 million metric tons of lithium are calculated to be present in the brines of the Smackover Formation in southern Arkansas. The range in possible total lithium reflects the uncertainty in machine-learning predictions of lithium concentrations and the range of Smackover Formation porosity. This estimate quantifies the in-place lithium resource and does not consider the technological and economic feasibility of extracting the lithium from the brines.

Arkansas↗

USGS2024

Ion exchange processes for CO2 mineralization using industrial waste streams: Pilot plant demonstration and life cycle assessment

An attractive technique for removing CO 2 from the environment is sequestration within stable carbonate solids (e. g., calcite). However, continuous addition of alkalinity is required to achieve favorable conditions for carbonate precipitation (pH>8) from aqueous streams containing dissolved CO 2 (pH<4.5) and Ca 2+ ions. In this study, a pH-swing process using ion exchange was demonstrated to process 300 L of produced water brine per day for CO 2 mineralization. Proton titration capacities were quantified for aqueous streams in equilibrium with gas streams at various concentrations of CO 2 (pCO 2 =0.03–0.20 atm) and at various flow rates (0.5–2.0 L min −1 ). Energy intensities for the process were determined to be between 30 and 65 kWh per tonne of CO 2 sequestered depending on the composition of the brine stream. A life cycle assessment was performed to analyze the net carbon emissions of the technology which indicated a net CO 2 reduction for pCO 2 ≥0.12 atm (−0.06–−0.39 kg CO 2 e per kg precipitated CaCO 3 ) utilizing calcium-rich brines. The results from this study indicate the ion exchange process can be used as a scalable method to provide alkalinity necessary for the capture and storage of CO 2 in Ca-rich waste streams.

Chemistry Select↗

USGS2024

Evaluation of coal mine drainage and associated precipitates for radium and rare earth element concentrations

Coal mine drainage (CMD) and associated metal-rich precipitates have recently been proposed as unconventional sources of rare earth elements (REEs). However, the potential occurrence of radium (Ra), a known carcinogen, with the REE-bearing phases has not been investigated. We hypothesized that Ra may occur in solids that are precipitated from CMD as a “radiobarite” solid solution ((Ba,Sr,Ra)SO 4 ) and/or adsorbed with hydrous metal oxides. REEs have been documented to sorb or co-precipitate with iron (Fe), manganese (Mn), and aluminum (Al) oxyhydroxide in CMD solids. Likewise, Ra has been documented to sorb to hydrous Fe and Mn oxides especially where sulfate (SO 4 ) and/or barium (Ba) concentrations are insufficient to precipitate radiobarite. Thus, we conducted the first-ever survey of Ra concentrations in corresponding CMD water and solid samples in the United States. Samples were analyzed from 4 untreated and 9 treated CMD sites in both the bituminous and anthracite coal regions of Pennsylvania across a range of pH and SO 4 concentrations. The dissolved Ra in CMD was relatively low (<0.5 Bq/L), consistent with radiobarite solubility; however, CMD solids were largely composed of amorphous Fe, Al, and Mn oxyhydroxide and silicate minerals. Ra was associated with Mn-enriched CMD solids, upwards of 875 Bq/kg. Total REE + yttrium (Y) content in the CMD solids was enriched upwards of 3600 mg/kg and was significantly correlated with Al content. These preliminary results suggest that REE extraction may target Al-rich solids to avoid Ra in Mn-rich solids.

Pennsylvania↗

USGS2024

Utica/Point Pleasant brine isotopic compositions (δ7Li, δ11B, δ138Ba) elucidate mechanisms of lithium enrichment in the Appalachian Basin

Global Li production will require a ~500 % increase to meet 2050 projected energy storage demands. One potential source is oil and gas wastewater (i.e., produced water or brine), which naturally has high total dissolved solids (TDS) concentrations, that can also be enriched in Li (>100 mg/L). Understanding the sources and mechanisms responsible for high naturally-occurring Li concentrations can aid in efficient targeting of these brines. The isotopic composition (δ 7 Li, δ 11 B, δ 138 Ba) of produced water and core samples from the Utica Shale and Point Pleasant Formation (UPP) in the Appalachian Basin, USA indicates that depth-dependent thermal maturity and water-rock interaction, including diagenetic clay mineral transformations, likely control Li concentrations. A survey of Li content in produced waters throughout the USA indicates that Appalachian Basin brines from the Marcellus Shale to the UPP have the potential for economic resource recovery.

Maryland, Ohio, Pennsylvania, West Virginia↗

USGS2024

Produced water geochemistry from hydraulically stimulated Niobrara Formation petroleum wells: Origin of salinity and temporal perspectives on treatment and reuse

Produced water (i.e., a mixture of returned injection fluids and geologic formation brines) represents the largest volumetric waste stream associated with petroleum production in the United States. As such, produced water has been the focus of intense study with emphasis on understanding the geologic origin of the fluids, environmental impacts of unintended or intentional release, disposal concerns, and their commodity (e.g., lithium) potential. However, produced water geochemistry from many active petroleum plays remain poorly constrained leading to knowledge gaps associated with the origin of brine salinity and parameters (e.g., radium levels) that can impact treatment, disposal, and possible reuse. Here we evaluate the major ion geochemistry, radium concentrations, and stable water isotope composition of ~120 produced water samples collected from 17 producing unconventional petroleum wells in Weld County, Colorado from the Late Cretaceous Niobrara Formation. This sample set encompasses eight produced water time series from four new wells across production days 0 to ~365 and from four established wells across production days ~1000 to ~1700. Additionally, produced water from nine other established Niobrara Formation wells were sampled at discrete time points ranging from day 458 to day 2256, as well as hydraulic fracturing input fluids. These results expand the available Niobrara Formation produced water geochemical data, previously limited to few wells sampled within the first year of production, allowing for the heterogeneity of major ions and radium to be evaluated. Furthermore, we explore the geochemical relationships between major ion ratios and stable water isotope composition to understand the origin of salinity in Niobrara Formation brines from the Denver-Julesburg Basin. These findings are discussed with perspective toward potential treatment and reuse of Niobrara produced water prior to disposal.

Colorado, Nebraska, Wyoming↗

USGS2024

Evaluation of the lithium resource in the Smackover Formation brines of southern Arkansas using machine learning

Global demand for lithium, the primary component of lithium-ion batteries, greatly exceeds known supplies, and this imbalance is expected to increase as the world transitions away from fossil fuel energy sources. High concentrations of lithium in brines have been observed in the Smackover Formation in southern Arkansas (>400 milligrams per liter). We used published and newly collected brine lithium concentration data to train a random forest machine-learning model using geologic, geochemical, and temperature explanatory variables and create a map of predicted lithium concentrations in Smackover Formation brines across southern Arkansas. Using these predicted lithium maps with reservoir parameters and geologic information, we calculated that there are 5.1 to 19 million tons of lithium in Smackover Formation brines in southern Arkansas, which represents 35 to 136% of the current US lithium resource estimate. Based on these calculations, in 2022, 5000 tons of dissolved lithium were brought to the surface within brines as waste streams of the oil, gas, and bromine industries.

Arkansas↗

USGS2022

Dissolved organic matter within oil and gas associated wastewaters from U.S. unconventional petroleum plays: Comparisons and consequences for disposal and reuse

Wastewater generated during petroleum extraction (produced water) may contain high concentrations of dissolved organics due to their intimate association with organic-rich source rocks, expelled petroleum, and organic additives to fluids used for hydraulic fracturing of unconventional (e.g., shale) reservoirs. Dissolved organic matter (DOM) within produced water represents a challenge for treatment prior to beneficial reuse. High salinities characteristic of produced water, often 10× greater than seawater, coupled to the complex DOM ensemble create analytical obstacles with typical methods. Excitation-emission matrix spectroscopy (EEMS) can rapidly characterize the fluorescent component of DOM with little impact from matrix effects. We applied EEMS to evaluate DOM composition in 18 produced water samples from six North American unconventional petroleum plays. Represented reservoirs include the Eagle Ford Shale (Gulf Coast Basin), Wolfcamp/Cline Shales (Permian Basin), Marcellus Shale and Utica/Point Pleasant (Appalachian Basin), Niobrara Chalk (Denver-Julesburg Basin), and the Bakken Formation (Williston Basin). Results indicate that the relative chromophoric DOM composition in unconventional produced water may distinguish different lithologies, thermal maturity of resource types (e.g., heavy oil vs. dry gas), and fracturing fluid compositions, but is generally insensitive to salinity and DOM concentration. These results are discussed with perspective toward DOM influence on geochemical processes and the potential for targeted organic compound treatment for the reuse of produced water.

Colorado, Montana, Nebraska, New York, North Dakot↗

USGS2019

Radium accumulation in carbonate river sediments at oil and gas produced water discharges: Implications for beneficial use as disposal management

In the western U.S., produced water from oil and gas wells discharged to surface water augments downstream supplies used for irrigation and livestock watering. Here we investigate six permitted discharges on three neighboring tributary systems in Wyoming. During 2013-16, we evaluated radium activities of the permitted discharges and the potential for radium accumulation in associated stream sediments. Radium activities of the sediments at the points of discharge ranged from approximately 200-3600 Bq/kg with elevated activities above the background of 74 Bq/kg over 30 km downstream of one permitted discharge. Sediment as deep as 30 cm near the point of discharge had radium activities elevated above background. X-ray diffraction and targeted sequential extraction of radium in sediments indicate that radium is likely coprecipitated with carbonate, and to a lesser extent sulfate minerals. PHREEQC modeling predicts radium coprecipitation with aragonite and barite, but over-estimates the latter compared to observations of downstream sediment, where carbonate predominates. Mass-balance calculations indicate over 3 billion Bq of radium activity (226Ra+228Ra) is discharged each year from five of the discharges, combined, with only 5 percent of the annual load retained in stream sediments within 100m of the effluent discharges; the remaining 95 percent of the radium is transported farther downstream as sediment-associated and aqueous species

Environmental Science↗

USGS2018

Radium attenuation and mobilization in stream sediments following oil and gas wastewater disposal in western Pennsylvania

Centralized waste treatment facilities (CWTs) in Pennsylvania discharged wastewater from conventional and unconventional oil and gas (O&G) wells into surface waters until 2011, when a voluntary request from the Pennsylvania Department of Environmental Protection (PA DEP) encouraged recycling rather than treating and discharging unconventional O&G wastewater. To determine the effect of this request on the occurrence of radium in streams, we sampled sediments at five CWTs that processed conventional O&G wastewater from 2011 to 2017 and compared results to published data. Despite the policy change in 2011 that reduced disposal of unconventional wastes (i.e., Marcellus) to surface water in Pennsylvania, the continued disposal of conventional O&G wastewater led to elevated radium activities in sediments at the point of discharge that were often hundreds of times higher than background. While these elevated activities were also present in downstream sediments (1.5× higher than background), the elimination of unconventional O&G wastewater disposal through the CWTs since 2011 decreased radium loading to the stream by approximately 95%. Sequential extractions and geochemical modeling using PHREEQC indicate that radium likely co-precipitates with barite or barite-celestite solid solutions and accumulates in the sediment as treated O&G effluent enters the stream. Adsorption of “exchangeable” radium, barium , and strontium on hydrous iron and manganese oxide coatings on fine-grained stream sediments is an important radium sequestration mechanism further downstream that can decrease the cation concentrations and potential for radio-barite co-precipitation. Radium downstream of CWTs was more abundant and more available for dissolution and desorption than radium in upstream sediments.

Pennsylvania↗