Physical Sciences and Mathematics Commons^™

Environmental Fate Of Sulfur In Sulphur Creek, Valles Caldera, Nm: Implications For Metal Transport And Water Quality, Daniel Lavery

Earth and Planetary Sciences ETDs

The 1.2 Ma Valles Caldera in north-central New Mexico hosts a young igneous volcanic hydrothermal system after the model proposed in Goff and Janik (2000). The Sulphur Springs area within Valles Caldera is an acid-sulfate area typical of this model, discharging acidic waters (pH 1.5-3) formed by oxidation of magmatic H₂S at the surface. We report on samples obtained from springs and streams collected between October 2021 and May 2023 in the Sulphur Creek and Alamo watersheds. Sulphur Creek receives input from Sulphur Springs and exhibits low pH (2-4) and high concentrations of Al (≤110 mg/L), Fe (≤60 …

A Rapid High-Precision Analytical Method For Triple Oxygen Isotope Analysis Of Co2 Gas Using Tunable Infrared Laser Direct Absorption Spectroscopy, Nathan Perdue, Zachary Sharp, David Nelson Jr., Rick Wehr, Christoph Dyroff

Earth and Planetary Sciences ETDs

Rationale

The simultaneous analysis of the three stable isotopes of oxygen – triple oxygen isotope analysis – has become an important analytical technique in natural sciences. Determination of the abundance of the rare ¹⁷O isotope in CO₂ gas using magnetic sector isotope ratio mass spectrometry is complicated by the isobaric interference of ¹⁷O by ­¹³C (¹³C¹⁶O¹⁶O and ¹²C¹⁶O¹⁷O both have mass 45 amu). A number of analytical techniques have been used to measure the ¹⁷O/¹⁶O ratio of CO₂ gas. They …

Halogen And Non-Traditional Isotope Geochemistry Of Planetary And Terrestrial Materials, Anthony Gargano, Zachary Sharp, Justin Simon, Charles Shearer, Adrian Brearley, James Day

Earth and Planetary Sciences ETDs

This dissertation presents the advances in non-traditional isotope geochemistry of planetary and terrestrial materials encompassing chlorine, sulfur, and zinc isotopes, as well as halogen geochemistry. A wide breadth of materials was studied throughout the completion of this work including iron meteorites, achondrites, chondrites, Apollo lunar samples, as well ancient marine chert, and carbonate sediments. Much of the focus involved the development of a method capable of simultaneously measuring the halogen contents and chlorine isotope compositions of geological materials. Here, I present these data sets to broadly characterize the process of devolatilization of planetary materials, and specifically the problem of ‘halogen-poisoning’ …

Using Triple Oxygen Isotopes To Reveal The Origin And Evolution Of Mantle Eclogite, Catherine Mary Peshek

Earth and Planetary Sciences ETDs

Triple oxygen isotope (TOI) measurements of mantle eclogite from the Orapa kimberlite pipe have reconstructed bulk rock '18O values from 4.587 to 9.542‰ (vs. VSMOW) and '17O from -0.075 to -0.044‰ (vs. VSMOW,  ~0.528). TOI values show increasing '18O with decreasing '17O, overlapping with modern measured altered oceanic crust. Orapa eclogite xenoliths with alkali enrichments show variable mantle-like and heavy 18O, consistent with subduction of seafloor altered basalt. Na# (Na/Na+Ca) in clinopyroxene for some xenoliths pairs with mantle-like oxygen, variable and extreme LREE enrichment, elevated Mg# and lower jadeite contents. These samples preserve records of eclogite melting, mantle interaction …

Petrology And Geochemistry Of Evolved Achondrites: Planetesimal Mantles And Crusts, Zoltan Vaci

Earth and Planetary Sciences ETDs

Melting and differentiation are fundamental to early solar system evolution on planetary bodies that accreted enough material to heat up radioactively or through impacts and breach their solidi. Partially and fully melted material is present in the meteorite record in the form of primitive achondrites and achondrites, which are fragments of planetesimals that underwent heating events in the first few million years of solar system history. Although the vast majority of this material is mafic or ultramafic, new evolved samples, recovered in the last few decades, are pushing the petrologic and geochemical boundaries of planetesimal melting, differentiation, and crust formation. …

A Triple Oxygen Isotope Analysis Of Altered Oceanic Crust And Its Buffering Effect On The Steady State Oxygen Isotope Composition Of Seawater, Jesse P. Mcgunnigle

Earth and Planetary Sciences ETDs

The secular chemical marine sediment trend showing an increase in δ¹⁸O over geologic time has traditionally been investigated using δ¹⁸O modelling of ancient ocean compositions, ocean surface temperatures, and sample diagenetic alteration. This study presents a triple oxygen isotope mass balance for the oceans using high precision δ¹⁸O and Δ'¹⁷O measurements of altered oceanic crust. The mass balance model predicts an ice-free seawater with δ¹⁸O = -0.29‰ and Δ’¹⁷O = -0.002‰ with steady state reached at approximately (0.5 to 1)×10⁹ years. Modifications to the hydrothermal alteration and …

Diversity – Independent Factors Predict Elevated Extinction Rates, Dustin Perriguey, Corinne Myers, Jason Moore, Louis Scuderi

Earth and Planetary Sciences ETDs

Multiple linear regression was used to determine the relationships between diversity-independent factors (i.e., abiotic, climatic) 2, 5, and 10 Myrs-prior to the most elevated Phanerozoic extinctions. We constructed five abiotic variables from Phanerozoic proxy records1–5 to compare to extinction rates: mean temperature, temperature instability, carbon cycle instability, continental weathering rates, and habitat instability. All three models were statistically significant (P < 0.05) and explained > 70% of the variation in Alroy’s6 three-timer generic extinction rates. However, the 2 Myr-prior model explained the most variance in extinction rates and had the most predictive power, based on adjusted and predictive R2 (~ 72% and 41%, respectively). Carbon …

Microstructural And Microchemical Studies Of Fluid–Chondrule Interactions In A Pristine Cr Carbonaceous Chondrite And Apatite In Martian Nakhlites, Marina Martínez

Earth and Planetary Sciences ETDs

PROJECT 1: Chondrites are the most primitive objects in the solar system, aggregates of the material that formed in the solar protoplanetary disk during the first 1-5 million years of its formation. However, petrographic observations indicate that most chondrites have been modified by secondary processes, including aqueous alteration, thermal metamorphism, and shock. Fortunately, a few chondrites largely escaped these processes and are considered pristine, such as the CR carbonaceous chondrite Queen Alexandra Range (QUE) 99177. QUE 99177 is an excellent sample for deciphering information about the reactions that took place between unaltered anhydrous solar nebular components and water under highly …

Boron Adsorption In Clay Minerals: Implications For Martian Groundwater Chemistry And Prebiotic Processes, Matthew A. Nellessen, Laura Crossey, Patrick J. Gasda, Horton Newsom, Abdulmehdi Ali, Eric J. Peterson, Nina Lanza, Adriana Reyes-Newell, Dorothea Delapp, Chris Yeager, Andrea Labouriau, Roger C. Wiens, Samuel Clegg, Shelbie Legett, Debarati Das

Earth and Planetary Sciences ETDs

Boron has been detected on Mars [Gasda et al., 2017, Das et al., 2019, 2020] within calciumsulfate veins found within clay-rich rocks on Mars by the Mars Science Laboratory (MSL) rover using Laser Induced Breakdown Spectroscopy (LIBS) analysis. Boron plays a vital role in stabilizing ribose on Earth and has been suggested as a key requirement for life [Scorei et al., 2006, 2012; Furukawa et al., 2013, 2017; Becker et al., 2019]. Additionally, boron readily adsorbs to phyllosilicate clay minerals and is often associated with biologic processes in clay soils. The discovery of boron on Mars in proximity to phyllosilicate …

Triple Oxygen Isotope Composition Of Carbonates, Jordan A.G. Wostbrock

Earth and Planetary Sciences ETDs

This dissertation presents a method of analyzing the triple oxygen isotope compositions of carbonates, presents an empirical calibration of the carbonate-water equilibrium fractionation line, presents a triple oxygen isotope equipped fluid-rock mixing model for carbonates to see-through diagenesis, and applies all these findings to ancient carbonate samples. Using modern carbonates and associate water, the following equations are calculated to describe equilibrium triple oxygen isotope fractionation of carbonates:

1000lnalpha¹⁸O_cc-wt=2.84x10⁶/T²-2.96 1),

Theta_cc-wt=-1.39/T+0.5305 2).

Using these fractionation equations provides an extremely useful tool to determine whether a carbonate sample is altered or preserves …

Constraining The Oxygen Values Of The Late Cretaceous Western Interior Seaway Using Marine Bivalves, Camille H. Dwyer

Earth and Planetary Sciences ETDs

The Western Interior Seaway (WIS) remains an oceanographic enigma, including its circulation, similarity to the open ocean, and the fidelity of geochemical proxies to reconstruct paleoenvironments. Across the late Campanian and early Maastrichtian I test whether: 1) the WIS had unique δ¹⁸O_VPDB compared to other marine settings, 2) increasing oceanographic restriction changed the stable isotope composition, and 3) biases, e.g., taxonomy or diagenesis, influenced stable isotope compositions. Results indicate distinct δ¹⁸O_VPDB in the WIS compared to other marine settings. δ¹⁸O_VPDB values were stable through time, suggesting insignificant oceanographic restriction and a …

Natural Salinization Of The Jemez River, New Mexico: An Insight From Trace Element Geochemistry, Jon K. Golla

Earth and Planetary Sciences ETDs

The Jemez River, a tributary of the Rio Grande in north-central New Mexico, receives thermal water input from the geofluids of the Valles Caldera, an active, high-temperature, liquid-dominated geothermal system. We focus on a ∼50-km portion of the northern Jemez River. This research extends previous decadal work (Crossey et al., in prep., 2013) on major chemistry in the river by characterizing the response of 16 trace elements to geochemical contributions from geothermal waters (McCauley, Spence, Soda Dam, and Jemez Springs springs and San Ysidro mineral waters), an area with copious hydrothermal degassing (Hummingbird), and two major tributaries (Rio San Antonio …

An Estimation Of Lower Tropospheric Mixing Derived From Inverse Modeling Of Boundary Layer Water Vapor Isotopologues On Graciosa Island, Azores, Jacquelyn M. Delp

Earth and Planetary Sciences ETDs

Recent studies have shown water vapor isotopologues to be sensitive tracers of mixing processes that govern low-cloud feedback in climate models. In this study, we develop an inverse model (MBL Mix inverse model) that uses one year of isotope and humidity observations from Graciosa Island, Azores to estimate mixing for four seasons. We show the dry end-member of the model, the lower free troposphere (LFT), can be represented using Rayleigh fractionation. Isotope observations from Graciosa Island are compared to other field locations to discuss controls on isotopic variability other than mixing. Output from the MBL Mix inverse model shows the …

Mantle-To-Surface Neotectonic Connections In The San Juan Mountains Documented By 3he/4he, Co2 Flux Meaurements, And Hydrochemical Analysis Of The Geothermal System Near Rico, Colorado, Benjamin D. Holt

Earth and Planetary Sciences ETDs

This project investigates the controls on geothermal fluids and their conduit systems which may account for high mantle helium components of geothermal fluids in intracratonic continental regions. The field laboratory is the western San Juan Mountains of southwestern Colorado where the structural setting and hydrochemistry of carbonic springs suggest potential connections among surface hot springs, fault networks, CO2 degassing, significant geothermal potential, young volcanic and plutonic rocks (< 7 Ma), and low-velocity upper mantle. The Rico Hot Springs have the highest mantle volatile component of any spring in Colorado with air-corrected values of 3He/4He = 5.88 RA indicating 73% mantle helium component. This near-MORB mantle helium value at Rico indicates that volatiles degassing from the mantle must be rapidly transmitted into the groundwater system along deep-seated faults such that accumulation of 4He from radiogenic crust has not swamped mantle-derived primordial 3He. Geologic features that are important for volatile transport and spring chemistry controls include a complex conduit system and fault network involving the Precambrian-cored Rico Dome, ~4 Ma intrusive rocks at Calico Peak and Priest Gulch, and a low-velocity upper mantle. Therefore, Rico and the surrounding region is a natural laboratory for studying geothermal fluid and mantle volatile pathways. Additional noble gas analyses and hydrochemistry data were gathered from regional springs and modeled via chemical geothermometers. New noble gas measurements from this study, paired with literature values, reveal highest air corrected 3He/4He at Rico (4.09-5.88 RA), Dunton (3.11-4.54 RA), Geyser Warm Spring (3.39 RA), and Paradise Warm Spring (2.72 RA). Water volume is dominated by meteoric fluids as shown by stable isotope data but hydrochemistry indicates high TDS, high CO2, and high He come from a geothermal fluid endmember. Variable mixing and water-rock interactions are processes that can explain chemistry variations between spatially proximal springs. CO2 flux measurements (up to 36.2 g/m2/hr) vary across structural features and demonstrate that the faults act as pathways for CO2 flux suggesting ongoing degassing. Overall, we find that local high mantle helium signature is localized directly above regions of lowest upper mantle velocity in the San Juan mantle anomaly and is derived from neotectonic mantle melts in those regions.

Use Of Sodium Dithionite For Groundwater Restoration Following Uranium In-Situ Recovery Mining At The Smith Ranch-Highalnd Site In Wyoming, Rose J. Harris

Earth and Planetary Sciences ETDs

Uranium in-situ recovery (ISR) is a subsurface aqueous mining technique used to extract uranium from sandstone roll-front deposits. After ISR mining, groundwater restoration is conducted to decrease concentrations of residual U(VI) and other contaminants leftover in the groundwater. Sodium dithionite, a strong chemical reductant, is being tested for use in groundwater restoration following uranium ISR at the Smith Ranch-Highland site in Wyoming. Sodium dithionite has been used to remediate chromium plumes by creating an in-situ permeable reactive barrier, but there has been no work using sodium dithionite for groundwater restoration following uranium ISR mining.

Laboratory batch and column experiments, and …

Crustal Seismic Anisotropy Of The Ruby Mountains Core Complex And Surrounding Northern Basin And Range, Justin T. Wilgus

Earth and Planetary Sciences ETDs

Metamorphic core complexes (MCC) are distinctive uplifts that expose deeply exhumed and deformed crustal rocks due to localized extensional deformation. Consequently, their detailed structure provide a window into deep crustal mechanics. The North American Cordillera contains numerous MCC, one of which is the Ruby Mountains core complex (RMCC) located in the highly extended northern Basin and Range. To constrain the extent to which anisotropy below the RMCC deviates from the regional Basin and Range average and test the depth dependence of crustal anisotropy we conduct a radial anisotropy investigation below the RMCC and surrounding northern Basin and Range. Data from …

Global Seawater Redox Trends During The Late Devonian Mass Extinction Detected Using U Isotopes Of Marine Carbonates, David Allen White

Earth and Planetary Sciences ETDs

The Late Devonian extinction ranks as one of the ‘big five’ Phanerozoic extinctions affecting up to 80% of marine species and occurred during five distinct pulses spanning /or widespread marine anoxia. We test the marine anoxia hypothesis by analyzing uranium isotopes (δ²³⁸U) across a ~7 My interval of well-dated Upper Devonian marine carbonates from the Devil’s Gate Limestone in Nevada, USA.

The measured δ²³⁸U curve shows no co-variation with local anoxic facies, water-depth dependent facies changes, redox-sensitive metals, TOC, or diagnostic elemental ratios indicating the δ²³⁸U curve was not controlled by local depositional or …

Geochemistry Of Volatiles Released By Incipient Continental Rifting And Subduction Processes, Hyunwoo Lee

Earth and Planetary Sciences ETDs

Volatiles (N2, CO2, and He) are released by volcanism and hydrothermal activity during continental rifting and subduction processes. Analyses of volatile components have been conducted to obtain gas contents (CO2, SO2, H2S, N2, Ar, He, and so on), stable isotope compositions (δ13C, δ15N, and so on), and noble gas isotopes (3He/4He, 40Ar/36Ar, and so on). This dissertation includes four chapters to report new nitrogen isotope fractionation factors of bubbling gases during gas-water transfer at various water temperatures (Chapter 1), first measurements of massive amounts of CO2 released by incipient continental rifting in the Magadi and Natron Basin, East African Rift …

Magmatic Hydrothermal Alteration And Secondary Post-Shock Features In Martian Olivine-Phyric Basalt Northwest Africa 10416; Petrology And Geochemistry Of Primitive Achondrite Northwest Africa 11042, Zoltan Vaci

Earth and Planetary Sciences ETDs

The Martian olivine-phyric basalt Northwest Africa (NWA) 10416 contains large olivine xenocrysts whose cores have been stained brown by hydrothermal alteration and whose rims are composed of pristine olivine overgrowths. Microanalysis of these olivine cores reveals various degrees of amorphization, some of which have been overprinted by terrestrial weathering, evident as part of a weathering rind along the exposed surface of the meteorite. Studies of a completely unweathered terrestrial analogue basalt from southern Colorado reveal similar features and indicate that both basalts were altered in a supersolidus magma chamber setting. The alteration features in NWA 10416 thus imply the presence …

Abrupt Ocean Anoxia During The Late Ordovician Mass Extinction Detected Using Uranium Isotopes Of Marine Carbonates, Rickey Bartlett, Maya Elrick, Yemane Asmerom, Viorel Atudorei

Earth and Planetary Sciences ETDs

The Ordovician witnessed an explosion in marine biodiversity punctuated by the first of the ‘big-5’ Phanerozoic mass extinctions, the Late Ordovician mass extinction (LOME). The LOME consists of two discrete pulses occurring at the beginning and end of the Hirnantian. Lithologic and geochemical evidence suggests widespread marine anoxia triggered the second LOME pulse; however, most of these redox proxies record local bottom water or porewater conditions rather than global seawater conditions. To evaluate global redox trends, we utilize uranium (U) isotopes and trace element geochemistry of marine carbonates as a global marine redox proxy.

Bulk carbonate samples were collected from …