Geochemistry Commons^™

The Legacy Of Mining In Southwest Missouri: Past And Present Conditions Of The Tri-State Mining District, Anastasia M C Mcclanahan

Graduate Theses/Dissertations

The historic Tri-State Mining District (TSMD) of southwestern Missouri, southeastern Kansas, and northeastern Oklahoma has a history of lead and zinc mining that extended over a hundred years. During the district’s peak production period, the TSMD was one of the world’s largest producers of lead and zinc. The mining activities in the TSMD produced economic growth that supported the local communities and were essential to the victory of the Allied Forces during World War I and World War II. Beginning in the 1920s, the mining activities in the district slowly began to cease due to depletion of metal ores and …

Phosphorus Variability In The Area Of Influence Of The Mid-Barataria Sediment Diversion, Peter Mates

LSU Master's Theses

Man-made levees along the lower Mississippi River prevent delivery of sediment from building and maintaining Louisiana’s coastal wetlands. The Mid-Barataria sediment diversions is designed to reintroduce Mississippi River water, sediment, and nutrients into the sediment-starved Barataria Basin. Phosphorus (P) is an important macronutrient for regulating primary production in coastal marine ecosystems. Wetlands can serve as a sink or source for phosphorus to the overlying water column through various retention and release processes, dependent on concentration. Louisiana coastal systems can be phosphorus limited due to much higher concentrations of bioavailable Nitrogen in river water. The high soluble molar N:P ( >50:1) …

Geochemical Tracers Of Arctic Ocean Processes: A Study Of Gallium, Barium, And Vanadium, Laura M. Whitmore

Dissertations

The Arctic Ocean is linked to the global oceans and climate through its connectivity with the North Atlantic Ocean and the regional thermohaline deep water formation sites. It’s also a region undergoing rapid environmental change. To inform the community of potential changes in geochemical and biogeochemical cycles, this dissertation addresses three dissolved geochemical tracers (gallium, barium, and vanadium) as indicators of Arctic Ocean processes. Gallium is tested as a replacement for nutrient-type tracers in an effort to deconvolve Pacific and Atlantic derived waters in the Arctic Ocean basins. These water masses carry different heat and salt content and can influence …

Reconstructing Hydrologic Conditions And Metals Supplied By The Peace River To The Peace-Athabasca Delta, Jelle André Faber

Theses and Dissertations (Comprehensive)

The Peace-Athabasca Delta (PAD) in northern Alberta, Canada, is recognized internationally for its ecological, historical, and cultural significance. The delta is mostly within Wood Buffalo National Park, a UNESCO World Heritage Site, and is a Ramsar Wetland of International Importance. The construction of the WAC Bennett Dam (1967) and the Site C Dam (ongoing, 2024) on the Peace River, and expansion of the Alberta Oil Sands industry along the Athabasca River have raised concerns over water quantity and quality in the delta. When industry operations began, effective monitoring had not been implemented. Consequently, pre-industrial reference conditions are unknown and can …

Environmental Assessment Of Arsenic And Mercury Levels At The Garfield Mill Site, Calico, California, Steven Gregory Thorp

Electronic Theses, Projects, and Dissertations

Environmental impacts of mining at Calico, California, are poorly understood in comparison to the details of its history of silver production. Human health risks associated with arsenic from the lode rock, as well as mercury from the silver milling process, include central nervous system damage, organ failure, and death. To quantify the potential human health risk and manage remediation of this site, tailings from the Garfield Mill site were digitally mapped and chemically analyzed by portable x-ray fluorescence, which permitted volumetric estimates of total mill tailings and the arsenic and mercury budget, as well as identification of anomalies in the …

Environmental Forensic Characterization Of Former Rail Yard Soils Located Adjacent To The Statue Of Liberty In The New York/New Jersey Harbor, Diane Hagmann, Michael A. Kruge, Matthew Chi-Hymn Cheung, Maria Mastalerz, José Luis Gallego, Jay Prakash Singh, Jennifer Krumins, Xiaona N. Li, Nina M. Goodey

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Identifying inorganic and organic soil contaminants in urban brownfields can give insights into the adverse effects of industrial activities on soil function, ecological health, and environmental quality. Liberty State Park in Jersey City (N.J., USA) once supported a major rail yard that had dock facilities for both cargo and passenger service; a portion remains closed to the public, and a forest developed and spread in this area. The objectives of this study were to: 1) characterize the organic and inorganic compounds in Liberty State Park soils and compare the findings to an uncontaminated reference site (Hutcheson Memorial Forest); and 2) …

Seasonal Soil Carbon Fluxes In Transitioning Agricultural Soils In Central Washington State: Relations To Land-Use, Environmental Factors And Soil Carbon-Nitrogen Characteristics, Brandon Kautzman

All Master's Theses

Changing agricultural land-use practices to increase soil carbon sequestration contributes to climate change mitigation and improved food security by moving CO₂ from the atmosphere into soil as soil organic carbon (SOC). In 2016, a farm in Thorp, Washington, Spoon Full Farm, began converting land historically farmed using conventional methods of tillage and synthetic fertilizers to conservation farming methods with direct seeding and organic soil amendments with a goal of sequestering carbon in the soil. This project evaluates relationships of soil CO₂ respiration and net ecological exchange (NEE) with land-use types, seasonal environmental factors (air temperature, relative humidity, soil …

Groundwater Hydrogeolgy And Hydrochemistry Of Karst Springs In The Eastern Peninsula Of Fort Hood Military Installation, William Scribner Welles

Electronic Theses and Dissertations

The eastern peninsula of Fort Hood Military Installation is underlain by a complex karst spring network. These springs are a primary water source in a protected habitat for endangered songbirds, which has only recently begun to be fully investigated. These Fredericksburg Group springs express both epigenetic and hypogenetic karst signatures. The study area is part of a paleo reef trend, a hydraulically disconnected segment of the northern section of the Edwards Aquifer. This study utilized standard ion index values, repeated measures, and principal component analyses on the chemical profiles of six perennial springs to classify spring water sources and their …

High-Dimensional Isotope Relationships, Yuyang He

LSU Doctoral Dissertations

High-dimensional isotope relationships describes the relationships of two or more element or position-specific (PS) elements in the same molecule or ion. It provides us more powerful tools to study reaction mechanisms and dynamics. Chapter 1 is about dual or multiple stable isotope relationship on δ-δ (or δ'-δ') space. While temporal data sampled from a closed-system can be treated by a Rayleigh Distillation Model (RDM), spatial data should be treated by a Reaction-Transport Model (RTM). Here we compare the results of a closed-system RDM to a RTM for systems with diffusional mass transfer by simulating the trajectories on nitrate's δ'^{18 …}

Predicting Spatial Patterns In Precipitation Isotope (Δ2h And Δ18o) Seasonality Using Sinusoidal Isoscapes, Scott T. Allen, James W. Kirchner, Gregory R. Goldsmith

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Understanding how precipitation isotopes vary spatially and temporally is important for tracer applications. We tested how well month‐to‐month variations in precipitation δ18O and δ2H were captured by sinusoidal cycles, and how well spatial variations in these seasonal cycles could be predicted, across Switzerland. Sine functions representing seasonal cycles in precipitation isotopes explained between 47% and 94% of the variance in monthly δ18O and δ2H values at each monitoring site. A significant sinusoidal cycle was also observed in line‐conditioned excess. We interpolated the amplitudes, phases, and offsets of these sine functions across the landscape, using multiple linear …

Production And Composition Of Pyrogenic Dissolved Organic Matter From A Logical Series Of Laboratory-Generated Chars, Kyle W. Bostick, Andrew R. Zimmerman, Andrew S. Wozniak, Siddhartha Mitra, Patrick G. Hatcher

Chemistry & Biochemistry Faculty Publications

Though pyrogenic carbon (pyC) has been assumed to be predominantly stable, degradation and transfers of pyC between various pools have been found to influence its cycling and longevity in the environment. Dissolution via leaching may be the main control on loss processes such as microbial or abiotic oxidation, mineral sorption, or export to aquatic systems. Yet, little is known about the controls on pyrogenic dissolved organic matter (pyDOM) generation or composition. Here, the yield and composition of pyDOM generated through batch leaching of a thermal series of oak and grass biochars, as well as several non-pyrogenic reference materials, was compared …

Environmental Forensics Study Of Crude Oil And Petroleum Product Spills In Coastal And Oilfield Settings: Combined Insights From Conventional Gc-Ms, Thermodesorption-Gc-Ms And Pyrolysis-Gc-Ms, Michael A. Kruge, José Luis Gallego, Azucena Lara-Gonzalo, Noemi Esquinas

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

A representative set of five oil spill samples from four different regions displayed different product characteristics and different levels of weathering. Three of them were taken along shorelines affected by marine oil spill events, viz., Aboño and Prestige (Spain) and Deepwater Horizon (USA) and the other two were taken at inland oil spill sites (Angola and Kuwait). A multi-faceted environmental forensics approach revealed key molecular features. In addition to the conventional GC/MS analysis of saturated and aromatic fractions, the polar fractions also were analyzed, revealing a complex series of linear alkanones in those oil samples particularly enriched in aliphatics. Thermodesorption-GC-MS …

Stable Bromine Isotope Signature Of Bromoform From Enzymatic And Abiotic Formation Pathways And Its Application In Identifying Sources Of Environmental Bromoform In The Damariscotta River, Chengyang Wang

Honors Theses

Bromoform is a major source of atmospheric bromine. Most bromoform is produced by marine organisms including macroalgae and phytoplankton, using the enzyme bromoperoxidase (BPO). Bromoform can also be a byproduct of industrial processes such as water disinfection. Identifying sources of environmental bromoform is still a challenge. A novel technique of using quadrupole mass spectrometry coupled to a gas chromatography (GCqMS) was developed and optimized for Br isotope analyses. The study shows that GCqMS in single ion monitoring (SIM) mode can measure 81Br with precision of around ±0.7‰ (60pmol bromoform injected). This study aims to investigate stable Br isotopes of bromoform …

Comprehensive Silica Removal With Ferric Compounds For Industrial Wastewater Reuse, Ehren D. Baca

Civil Engineering ETDs

Cooling towers, integrated circuit (IC) manufacture and reverse osmosis (RO) generate copious amounts of wastewater high in colloidal and reactive silica inhibiting on-site or synergistic reuse. Silica present in cooling water can reach solubility limits via evaporation and form impervious scale on heat transfer surfaces that decreases efficiency. When water is treated by RO operating at high rejection, silica forms difficult-to-remove scale on the membrane feed side in the form of glassy patches and communities of aggregate particles, inhibiting aspirations for zero liquid discharge. Current methods for silica scale mitigation include abundant dosing with chemical antiscalents or complex operating schemes. …

Catalyzed Synthesis Of Zinc Clays By Prebiotic Central Metabolites, Marcelo I. Guzman, Ruixin Zhou, Kaustuv Basu, Hyman Hartman, Christopher J. Matocha, S. Kelly Sears, Hajatollah Vali

Chemistry Faculty Publications

How primordial metabolic networks such as the reverse tricarboxylic acid (rTCA) cycle and clay mineral catalysts coevolved remains a mystery in the puzzle to understand the origin of life. While prebiotic reactions from the rTCA cycle were accomplished via photochemistry on semiconductor minerals, the synthesis of clays was demonstrated at low temperature and ambient pressure catalyzed by oxalate. Herein, the crystallization of clay minerals is catalyzed by succinate, an example of a photoproduced intermediate from central metabolism. The experiments connect the synthesis of sauconite, a model for clay minerals, to prebiotic photochemistry. We report the temperature, pH, and concentration dependence …

A Miniaturized Spectrophotometric In Situ Ph Sensor For Seawater, Reuben C. Darlington

Graduate Student Theses, Dissertations, & Professional Papers

Since the Industrial Revolution, the world's oceans have absorbed increasing amounts of CO2 and the resultant changes to the marine carbonate chemical system have reduced the pH by > 0.1 units (~ 30%) in surface waters. This acidification of the oceans has many far reaching impacts on marine life and there is great need of quality instrumentation to assess and follow the changing carbonate system. This MIS project aims to develop a low cost pH sensor with high precision and accuracy for open sea measurements with special emphasis on reduced size and cost. Design effort is based on the commercially available …

A Complex Legacy Of Contamination In Urban Estuarine Systems, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Industrialized urban waterways have typically suffered decades of contamination, varying in source and intensity as manufacturing and transportation practices evolved. The U.S. Environmental Protection Agency designates locales with particularly severe contamination as Superfund sites. Among these, the Gowanus Canal and lower Passaic River in the New York/New Jersey harbor estuary illustrate a complex range of contamination types.

The 2.2 km Gowanus Canal, with sluggish circulation driven mostly by tides, accumulated fine-grained sediments (average thickness of 3 m) highly enriched in organic carbon (OC, mean 11 % but up to 49 %) derived from hydrocarbons, sewage, coal, char, and biomass, along …

The Role Of Organic Matter In The Surface Chemistry Of Arsenic Compounds On Iron−(Oxyhydr)Oxides Studied By Atr-Ftir, Arthur Situm

Theses and Dissertations (Comprehensive)

The interaction of organic matter with the interfaces of active soil components such as iron oxides is ubiquitous within soil environments. The presence of organics at these interfaces may have implications for other soil constituents whose mobility is controlled by their ability to bind to active soil components. Most of the studies performed to date which look at these interactions are bulk/batch studies performed ex-situ. Attenuated total internal reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was utilized within this work to study interactions between select model organics (citrate, oxalate and pyrocatechol) and iron−(oxyhydr)oxides, as well as their effect on the surface …

Seasonal Evolution Of Active Layer Formation In Subarctic Peat Plateaux And Implications For Dissolved Organic Matter Composition And Transfer, Jennifer L. Hickman

Theses and Dissertations (Comprehensive)

Peat-accumulating wetlands are ecosystems whose rate of photosynthetic production of organic matter is greater than that of its decomposition, resulting in a build up of soil organic matter that may take centuries to fully decompose. Carbon (C) stocks within these ecosystems are a function of inputs from photosynthesis, and losses from heterotrophic decomposition. Due to the short growing season and overall cold climate of boreal and tundra regions, C has been accumulating within these landscapes, mostly in soil organic matter, since the last glaciation. Climate change, predicted to result in rising temperatures and increased precipitation, has begun to degrade the …

Erratum To: Zn (Ii) And Cu (Ii) Adsorption And Retention Onto Iron Oxyhydroxide Nanoparticles: Effects Of Particle Aggregation And Salinity, Rebecca B. Chesne, Christopher S. Kim

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

In the original version of this article errors in Figs. 5 and 9 were identified by the authors. The corrected figures are given.

Using Nitrate, Chloride, Sodium, And Sulfate To Calculate Groundwater Age, Kimm Crawford, Terry Lee

Sinkhole Conference 2015

Regression analysis is used to identify monotonic trends to assign water age using ion data from two large well water databases from southeast Minnesota (SE MN). Nitrate (NO3-N), chloride (Cl), sodium (Na), and sulfate (SO4) ions in the commonly used aquifers in SE MN can be used as groundwater tracers since they are either entirely or partly anthropogenic in their sources, their loading occurs on a regional scale, and they are almost entirely conserved. Ion concentrations over time are used to establish six trend patterns. Two patterns are unchanging (background and stable above background), and four are changing (linear up, …

Pyrolysis-Gc-Ms For The Rapid Environmental Forensic Screening Of Contaminated Brownfield Soil, Azucena Lara-Gonzalo, Michael A. Kruge, I Lores, B Gutiérrez, José Luis Gallego

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

An abandoned chemical plant in Asturias (Spain) was studied using a multi-faceted molecular fingerprinting approach, demonstrating that it is possible to: (1) carefully unravel tangled evidence resulting from multiple pollution sources, and (2) recognize major contaminants largely ignored by conventional analyses. This methodology employed a battery of GC-MS analyses of liquid chromatographic fractions of soil extracts, plus the pyrolysis products of the soil extract's asphaltene fraction and the whole soil itself. In this example, coal tar distillation and the subsequent production of naphthalene, phenols and polymer resins are responsible for most of the soil contamination. Styrene, naphthalene, indene, and their …

Analytical Pyrolysis Principles And Applications To Environmental Science, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Over the past half century, analytical pyrolysis has proven itself to be an effective means for the semiquantitative characterization of complex macromolecular organic substances. It has been demonstrated that instruments such as Py-FID, Py-MS, and in particular, Py-GC/MS can provide valuable geochemical insights when applied to a wide variety of problems in environmental science. The more widespread use of analytical pyrolysis methods in the evaluation of environmental pollution is recommended, because of their relatively low cost and information-rich results.

Pyrolysis is the heating of organic substances in an inert, oxygen-free atmosphere, thereby avoiding combustion. When performed on a large scale, …

Iron Sources And Dissolved-Particulate Interactions In The Seawater Of The Western Equatorial Pacific, Iron Isotope Perspectives, M. Labatut, F. Lacan, C. Pradoux, J. Chmeleff, A. Radic, J. W. Murray, F. Poitrasson, Anne M. Johansen, F. Thil

All Faculty Scholarship for the College of the Sciences

This work presents iron isotope data in the western equatorial Pacific. Marine aerosols and top core margin sediments display a slightly heavy Fe isotopic composition (δ⁵⁶Fe) of 0.33 ± 0.11‰ (2SD) and 0.14 ± 0.07‰, respectively. Samples reflecting the influence of Papua New Guinea runoff (Sepik River and Rabaul volcano water) are characterized by crustal values. In seawater, Fe is mainly supplied in the particulate form and is found with a δ⁵⁶Fe between −0.49 and 0.34 ± 0.07‰. The particulate Fe seems to be brought mainly by runoff and transported across continental shelves and slopes. …

Ice Caves On Extraterrestrial Bodies: What Are The Prospects For Speleogenesis And Detection?, Penelope J. Boston

The International Workshop on Ice Caves

Potential mechanisms for creating cavities in icy extraterrestrial bodies have been tentatively explored by several authors. On one hand we have examples of mechanisms that create caves in water ice here on Earth. In addition, there may be unique mechanisms on other Solar System objects that do not occur on Earth but might produce cavities, e.g. sublimation of comets upon perihelion passage. The methods of detecting such cavities depend upon the nature of the icy body in question, the potential for orbital or landed missions to visit those bodies in the future, and remote or landed methods for detecting the …

Zn(Ii) And Cu(Ii) Adsorption And Retention Onto Iron Oxyhydroxide Nanoparticles: Effects Of Particle Aggregation And Salinity, Rebecca B. Chesne, Christopher S. Kim

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Background: Iron oxyhydroxides are commonly found in natural aqueous systems as nanoscale particles, where they can act as effective sorbents for dissolved metals due to their natural surface reactivity, small size and high surface area. These properties make nanoscale iron oxyhydroxides a relevant option for the remediation of water supplies contaminated with dissolved metals. However, natural geochemical processes, such as changes in ionic strength, pH, and temperature, can cause these particles to aggregate, thus affecting their sorption capabilities and remediation potential. Other environmental parameters such as increasing salinity may also impact metal retention, e. g. when particles are transported …

Surface Complexation Of Monosubstituted Organoarsenicals On Hematite: Atr-Ftir Investigations, Md Abdus Sabur

Theses and Dissertations (Comprehensive)

Little is known about the surface chemistry of organoarsenic compounds with iron-containing materials commonly found in geosorbents and arsenic removal technologies. In this thesis, these organoarsenicals include aliphatic and aromatic arsenicals that historically have been used as herbicides, pesticides and in the poultry feed industry, respectively. Attenuated total internal reflectance Fourier transform infrared spectroscopy has been used to study the surface interactions of organoarsenicals at the molecular level under various environmentally-relevant conditions. Kinetic and thermodynamic parameters extracted from these molecular level experiments provide trends that are not observed in any published bulk experiments. Apparent initial rates of adsorption and desorption …

Molecular Characteristics Of The Water Soluable Organic Matter In Size Resolved Aerosols Collected Over The North Atlantic Ocean, Sarah Catherine Gurganus

Chemistry & Biochemistry Theses & Dissertations

Aerosol particulate matter is acknowledged to have effects on health and the environment and further investigation into the molecular characteristics of aerosols is necessary in order to fully understand the potential links between the molecular characteristics and the impacts that these particles have on health and the environment. Aerosols are often discussed with reference to their size because particles of different sizes can often be associated with different primary sources. This study presents a molecular-level chemical characterization of the water soluble organic matter fraction of 17 aerosol impactor samples representing 3 air mass influences (North American, North African, and marine) …

Spectroscopic Study Of Uranium (Vi) Reduction By Plant Biomass, Margaret C. Murphy, John Bargar, Noémie Janot

STAR Program Research Presentations

Uranium is a common and problematic groundwater contaminant at Department of Energy legacy sites. At the former uranium ore processing plant at Rifle, Colorado, sediments rich in decayed plant biomass contain large concentrations of uranium that are slowly being released back to the aquifer. To simulate the reaction that occurs in organic rich sediments of the Rifle aquifer, biomass was incubated in U (VI) bearing groundwater. Carbon X-ray absorption spectroscopy (XAS) was then used to measure if uranium was bound to the biomass. When uranium binds to biomass the peaks in the C XAS spectra will change shape. Uranium L …

Oil Pollution In Water Bodies Of Restricted Circulation, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Coastal lagoons and embayments near urban centers around the world share many common characteristics and problems. Physical impediments to free water circulation (spits, barrier islands, internal islands, tombolos, submerged sills) often lead to water stagnation and, in the presence of excess nutrients, eutrophication. Urban and industrial activities provoke (usually accidental) spills of hazardous materials into these confined water bodies, such as crude petroleum and refined petroleum products, leading to difficulties for resident biota and potential hazards for human health. The sluggish turnover of these water bodies (or low-energy zones within them) may retard the natural attenuation of the spilled contaminants. …