Analytical Chemistry Commons^™

Molecular Evidence For The Export Of Terrigenous Organic Matter To The North Gulf Of Mexico By Solid-State 13C Nmr And Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Of Humic Acids, Sarah Ann Ware

Chemistry & Biochemistry Theses & Dissertations

Marine organic matter is mainly believed to originate from autochthonous organic matter, while terrigenous organic matter is assumed to be largely degraded prior to reaching the open ocean or more recently replaced by marine organic matter via a stripping process. Sediment samples along a transect extending from the Mississippi River Birdsfoot Delta to the Mississippi Canyon on the Louisiana continental shelf were examined by advanced analytical techniques, electrospray ionization coupled to a 12T Fourier transform ion cyclotron resonance mass spectrometer (ESI-FTICR-MS) and quantitative solid-state multiple cross polarization magic angle spinning (multi-CPMAS) ¹³C NMR in an effort to understand the …

Food Waste Storage Gaseous Emissions Detection And Quantification Using Infrared Spectroscopy, Ryley A. Burton-Tauzer

Cal Poly Humboldt theses and projects

A growing interest in sustainable waste management and the implementation of new policies have prompted a shift towards alternative resource recovery methods for organic waste, including food waste. To effectively assess alternative food waste treatment scenarios, it is important to evaluate the life cycle impacts associated with each scenario. The storage phase of food waste, encompassing its accumulation in kitchens, and storage in bins for collection and transportation, has been overlooked as a source of greenhouse gases in previous studies. This investigation aimed to identify the greenhouse gases emitted during the initial five-day period of low-oxygen storage. An open dynamic …

Computational And Experimental Investigations Of Alkali Cation Interactions At The Rutile – Water Interface, Isaac Johnston

All Dissertations

Overall, the objective of this dissertation was to investigate the degree of sorption for the alkali cations on rutile to ascertain the impact of different cation properties, such as ion size and charge density, on sorption mechanics as well as probe how the ion may alter the surface – aqueous interface. Initial molecular dynamic simulations and batch experiments showed minimal surface sorption for any alkali cation at relatively low concentrations while simultaneously suggesting the enthalpy of deprotonation shifts slightly in the presence of the alkali cations at different ionic strengths. The cations are likely causing small reorientations of the near-surface …

Concentration Of Heavy Metals In Three Distinct Algae Families From Humboldt County, California, Kodiak E. Miller, Caleb J. Strait, Jacob I. Begorre, Brittney L. Mitchell, Claire P. Till

IdeaFest: Interdisciplinary Journal of Creative Works and Research from Cal Poly Humboldt

Anthropogenic impacts on marine environments can impact metal fluxes and concentrations available to marine species. Monitoring these impacts is necessary to better understand the interactions between the biotic and abiotic components of these ecosystems and mitigate the risk posed by harmful toxins introduced by human activities. Biomoniters, like macroscopic algae, are useful indicators that illuminate the bioaccumulation of toxins commonly introduced from anthropogenic activity. With this in mind, the concentrations of heavy metals zinc (Zn), nickel (Ni), and copper (Cu) were analyzed via the assessment of algae (Representatives from Ulva, Mastocarpus, Fucus) in two sites in Humboldt County: …

Evaluation Of The Potential Of Automated Sem-Eds Analysis For The Discrimination Of Inorganic Soil Particles, Anna S. Duggar

Dissertations, Theses, and Capstone Projects

Soil, that complex mixture of minerals, organic particles, chemicals, and anthropogenic materials, is ubiquitous and easily transferred, which gives it forensic relevance. Forensic soil analysis has traditionally included the identification and comparison of both organic and inorganic components, the inorganic portion being most commonly examined by light microscopy and other instrumental techniques. Predominantly, the inorganic materials in soil are naturally-occurring minerals, contributed as grains from the surrounding bedrock, which gives a soil its regional character. That parent material then undergoes physical, chemical, and anthropogenic changes producing wide geographic variation within a single region. This variation forms the basis for potential …

Coastal Watershed Monitoring And Management: Geomorphology, Geochemistry, And Hydrologic Modeling Of Los Peñasquitos Creek, Ca, Ravleen Khalsa-Basra

Theses

Rivers in semi-arid climates are directly influenced by local geographic and hydrologic conditions and impacted by modifications to hydrology via urbanization. Changes can influence erosion, morphology, habitat sustainability, and watershed health. In highly urbanized southern California coastal regions, these rare open spaces provide vital ecosystem services. Los Peñasquitos Creek in San Diego County is one such watershed. Using stream surveying and laboratory methods we quantified channel characteristics, grain size distribution, total metal concentration [M], organic carbon (%OC), and phosphate to longitudinally characterize the creek for improved management. Results identified three distinct reaches in the watershed (upper, middle, lower). Downstream, depth …

The Quantitative Assessment Of Pond Scum: An Examination Of The Biogeochemistry Of Phosphorus Cycling In The Belgrade Lakes, Abbey M. Sykes

Honors Theses

The internal recycling phosphorus in freshwater lake bottom sediments represents a significant source of hypolimnetic phosphorus (P) release for many of Maine’s lakes. In summer months, Maine lakes often thermally stratify and the lake hypolimnion develops anoxia, leading to a reduction in redox potential at the sediment-water interface. These reducing conditions facilitate the reductive dissolution of ferric iron, and, since phosphorus is often present in freshwater lake sediments as solid FeOOH-PO₄ complexes, results in release of soluble phosphorus into the water column. Our current study presents field and laboratory data from sediment fractionation extractions designed to quantify concentrations of …

The Potential For Remote Sensing Measurement Of Dissolved Organic Carbon As A Tool For Metal Risk Assessments, Mickey Nielsen

Theses and Dissertations (Comprehensive)

The biotic ligand model (BLM) is a tool used to quantitatively evaluate how receiving water chemistry affects the bioavailability of metals. Sensitivity testing can be used to understand how the model outputs vary in response to systematic changes in water chemistry inputs. This will allow users of such models to understand how accurate their input parameters must be for a specified level of confidence in the output. Our focus was on dissolved organic carbon (DOC), which is often the most limiting data for application of BLM approaches to metals risk management. To potentially address DOC data limitations remote sensing can …

Structural Characterization Of Organic Matter In Oil Shales Using Multiple Nuclear Magnetic Resonance Spectroscopic Techniques, Wenying Chu

Chemistry & Biochemistry Theses & Dissertations

Oil shale is a promising source of hydrocarbon fuel that is distributed throughout the world. The petroleum generating potential of oil shale is related to the molecular structure of the organic matter in source rock. The major fraction of organic matter of oil shale is termed kerogen, and due to its insolubility in organic solvents, ¹³C solid-state nuclear magnetic resonance (NMR) spectroscopy is one of the best ways to directly measure the insoluble organic matter without changing its chemical structures. This dissertation investigated oil shale samples using advanced solid-state ¹³C NMR spectroscopy techniques and high resolution magic angle …

Assessment Of Soil Protein And Refractory Soil Organic Matter Across Two Chronosequences Of Newly Developing Marshes In Coastal Louisiana, Usa, Stuart Alexander Mcclellan

LSU Doctoral Dissertations

The impacts of sea-level rise and hydrologic manipulation are threatening the stability of coastal marshes throughout the world, thereby increasing the potential for re-mineralization of soil organic matter (SOM) in these systems. Such threats have prompted marsh restoration efforts, particularly in coastal Louisiana, yet it is unclear how the slowly decomposing (refractory) and quickly decomposing (labile) fractions of SOM may be differentially affected by different approaches to marsh restoration. Additionally, otherwise labile compounds may accumulate in the soil via a range of protective mechanisms, including rapid burial and association with organic compounds that are thought to enhance soil aggregation, such …

Characterization Of Coal Particles In The Soil Of A Former Rail Yard And Urban Brownfield: Liberty State Park, Jersey City (Nj), Usa, Diane F. Hagmann, Michael A. Kruge, Nina M. Goodey, Jennifer Adams Krumins

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

From the 1850's until the 1960's, the Central Railroad of New Jersey was among several major railways shipping anthracite and bituminous coal to the New York City area, transferring coal from railcar to barge at its extensive rail yard and port facility in Jersey City. The 490 ha Liberty State Park was developed on the site after the rail yard closed, but a ca. 100 ha brownfield zone within the park remains off limits to visitors pending future remediation. As part of an environmental forensic and industrial archeological investigation of this zone, the present study characterizes anthracite and bituminous coal …

Environmental Forensics Of Complexly Contaminated Sites: A Complimentary Fingerprinting Approach, Michael A. Kruge, Azucena Lara-Gonzalo, José Luis Gallego

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The environmental forensics approach is most often applied in petroleum and fuel spill incidents, for which sophisticated chemical fingerprinting procedures have evolved. In cases in which pollutant discharges occur in settings with prior contamination, more care must be taken in source discrimination, requiring further advances in methodology. Additional obstacles can arise if the spill is an atypical industrial discharge. This would necessitate painstaking characterization of unfamiliar substances lying outside of existing regulatory regimes and thus overlooked by mandated analytical protocols (i.e., contaminants of emerging concern). Towards these ends, this paper presents a systematic, multi-faceted GC-MS approach using the saturated, aromatic, …

Improving Thorium-230 Determination In Marine Sediment, Katherine Mateos

Independent Study Project (ISP) Collection

Our oceans are intimately related to the climate of our planet. Paleoceanographic approaches aim to study oceans through geologic time to improve models of future climate. Radioisotopes provide us with chemical tracers that help us understand change through time. The uraniumseries decay chain contains thorium-230, a decay product of uranium-234. This isotope is useful to paleoceanographers in its disequilibrium to its parent isotope and in determining the flux of sediment falling to the ocean floor. In order to use 230Th to study oceans, we must be able to accurately measure the amount of thorium in sediment samples. Thorium is found …

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) …

Compound-Specific Isotope Analysis Of Amino Acids In Biological Tissues: Applications In Forensic Entomology, Food Authentication And Soft-Biometrics In Humans, Mayara Patricia Viana De Matos

Graduate Theses, Dissertations, and Problem Reports

In this work we demonstrate the power of compound-specific isotope analysis (CSIA) to analyze proteinaceous biological materials in three distinct forensic applications, including: 1) linking necrophagous blow flies in different life stages to their primary carrion diet; 2) identifying the harvesting area of oysters for food authentication purposes; and 3) the ability to predict biometric traits about humans from their hair.

In the first application, we measured the amino-acid-level fractionation that occurs at each major life stage of Calliphora vicina (Robineau-Desvoidy) (Diptera: Calliphoridae) blow flies. Adult blow flies oviposited on raw pork muscle, beef muscle, or chicken liver. Larvae, pupae …

Characterization Of The Uranium-Bearing Phases Produced By Novel Remediation Technologies For Sequestration Of Mobile Radiological Contaminants In The Hanford 200 Area Vadose Zone, Robert Michael Lapierre

FIU Electronic Theses and Dissertations

Of the many toxic chemicals released into the Hanford vadose zone over the decades of nuclear weapons production, uranium has emerged as a contaminant of significant interest. The ammonia gas injection remediation method has been identified as a promising approach towards mitigating the risks to the ecosystem by limiting the mobility of the radionuclide in the vadose zone. The remediation method was replicated using synthetic porewater solutions with a range of constituent concentrations equal to that of the Hanford 200 Area vadose zone. The uranium-bearing products of the remediation method were characterized using kinetic phosphorescence analysis for aqueous uranium, scanning …

Advances In Amino Acid Analysis For Marine Related Matrices And Its Application To Coastal Shelf Settings In The Canadian Arctic, Rachel M. Mcmahon

OES Theses and Dissertations

Amino acids comprise up to 50% of organic matter in cellular material and are a major fraction of oceanic organic carbon. Amino acids are also considered highly labile during organic matter recycling, making them useful proxies for organic carbon cycling. Nevertheless, analysis of individual amino acids has been burdened by lengthy derivatization and complex analysis since the 1950s. In this thesis, I describe the modification of advanced analytical techniques, developed in the biomedical field, for analysis of marine matrices which allow the determination of at least 40 amino acids without the need for lengthy sample preparation and derivatization, twice the …

Detrital Protein Contributes To Oyster Nutrition And Growth In The Damariscotta Estuary, Maine, Usa, Cheyenne M. Adams

Electronic Theses and Dissertations

Oyster aquaculture is an expanding industry that relies on identifying and utilizing natural estuarine conditions for the economically viable production of a filter-feeding crop. The eastern oyster, Crassostrea virginica, is the principal species currently cultured in Maine. In addition to preferentially consumed phytoplankton, various detrital complexes (non-algal and/or non-living organic matter) may provide some nutrition to C. virginica between times of phytoplankton abundance. Here I investigated the importance of detrital proteins in supporting the growth of oysters cultured in the upper Damariscotta Estuary. Oyster aquaculture in this area is highly successful and previous reports indicate that labile detrital protein …

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 …

Alicyclic And Aromatic Carboxylic Acids In Soil Organic Matter: An Investigation Of Potential Origin And Association With Plutonium Using Advanced Analytical Techniques, Nicole Didonato

Chemistry & Biochemistry Theses & Dissertations

Carboxylic acids are a defining component of soil organic matter, responsible for many of the physical and chemical properties, including metal-organic matter interactions, which govern its role as an important constituent of soils. However, there is a shortage of detailed molecular level information regarding orientation and structural arrangement of carboxylic acids within soil organic matter. This dissertation utilizes electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) as well as solid-state and multi-dimensional nuclear magnetic resonance (NMR) to investigate the molecular formula composition within several organic matter sources and the primary structures that feature carboxylic acids. Soil organic matter …

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 …

Photocatalytic Reduction Of Fumarate To Succinate On Zns Mineral Surfaces, Ruixin Zhou, Marcelo I. Guzman

Chemistry Faculty Publications

The reductive tricarboxylic acid (rTCA) cycle is an important central biosynthetic pathway that fixes CO₂ into carboxylic acids. Among the five reductive steps in the rTCA cycle, the two-electron reduction of fumarate to succinate proceeds nonenzymatically on the surface of photoexcited sphalerite (ZnS) colloids suspended in water. This model reaction is chosen to systematically study the surface photoprocess occurring on ZnS in the presence of [Na₂S] (1–10 mM) hole scavenger at 15 °C. Experiments at variable pH (5–10) indicate that monodissociated fumaric acid is the primary electron acceptor forming the monoprotic form of succinic acid. The following …

The Marine Cyanate Cycle, Brittany Widner

OES Theses and Dissertations

Cyanate (OCN-) is a reduced nitrogen compound with the potential to serve as a nitrogen and carbon source for marine microbes. Evidence from genomes and culture studies indicated that several marine cyanobacterial groups, including representatives of the globally important genera Synechococcus and Prochlorococcus, might be capable of cyanate assimilation. However, prior to this study, the distribution, bioavailability, and production pathways of cyanate were unknown in natural systems due to the absence of a sensitive cyanate assay; and the ability of organisms to assimilate cyanate on relevant timescales was unknown because we lacked a suitable tracer for measuring uptake. I developed …

Measurement Of Antioxidant Activity Toward Superoxide In Natural Waters, D. Whitney King, Emma Berger, Zachary Helm, Eleanor Irish, Kenneth Mopper

Chemistry & Biochemistry Faculty Publications

Antioxidants are a class of molecules that provide a protective function against reactive oxygen species (ROS) in biological systems by out competing physiologically important molecules for ROS oxidation. In natural waters, the reactivity of antioxidants gives an estimate of oxidative stress, and may determine the reactivity and distribution of reactive oxidants. We present an analytical method to measure antioxidant activity in natural waters through the competition between ascorbic acid, an antioxidant, and MCLA, a chemiluminescent probe for superoxide. A numerical kinetic model of the analytical method has been developed to optimize analytical performance. Measurements of antioxidant concentrations in pure and …

Source-Specific Molecular Signatures For Light-Absorbing Organic Aerosols, Amanda Susan Willoughby

Chemistry & Biochemistry Theses & Dissertations

Organic aerosols (OA) are universally regarded as an important component of the atmosphere based on quantitative significance as well as the far-reaching impact they have on global climate forcing and human health. Despite the acknowledged importance, OA amounts and impacts remain the largest uncertainties regarding radiative forcing estimates. Incomplete chemical characterization of aerosol organic matter (OM) and a lack of concrete source apportionment is a major source of this uncertainty. The primary focus of this study is to provide much needed molecular details regarding ambient OA from key emission sources, and establish links between molecular and optical properties.

Complete chemical …

Field Scale Application Of Nanoscale Zero Valent Iron: Mobility, Contaminant Degradation, And Impact On Microbial Communities, Chris M.D. Kocur

Electronic Thesis and Dissertation Repository

This thesis began by verifying that nanoscale zero valent iron (nZVI) synthesis methods could be scaled up and implemented at the field scale in a safe manner. This led to successful demonstration of nZVI injection and mobility under constant head gravity injection into a contaminated utility corridor in Sarnia, Ontario. Where field studies have fallen short in the past was linking the somewhat qualitative field geochemical parameters to other evidence of nZVI transport. Definitive nZVI detection was elusive in previous field studies due to the highly reactive nature of the particles caused by their high surface area. nZVI was detected …

Nanodiamond Extraction At A Potential Impact Location, Joel Kathan

DePaul Discoveries

Meteoritic or cometary impacts create the temperature and pressure conditions necessary to form nanodiamonds (NDs). The presence of extracted NDs from rocks of the time and locations of extinctions, fires, or known environmental changes are commonly used to confirm that a theorized cosmic impact occurred to trigger those events. Samples were obtained from an archeological site described in the Old Testament of the Bible as having been destroyed by the God of the Old Testament.† To see if the historical description of Biblical events might have been triggered by a cometary impact or explosion, an attempt was made to …

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, …

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 …

Application Of Biomarkers And Compound Specific Stable Isotopes For The Assessment Of Hydrology As A Driver Of Organic Matter Dynamics In The Everglades Ecosystem, Ding He

FIU Electronic Theses and Dissertations

The Everglades is a sub-tropical coastal wetland characterized among others by its hydrological features and deposits of peat. Formation and preservation of organic matter in soils and sediments in this wetland ecosystem is critical for its sustainability and hydrological processes are important divers in the origin, transport and fate of organic matter. With this in mind, organic matter dynamics in the greater Florida Everglades was studied though various organic geochemistry techniques, especially biomarkers, bulk and compound specific δ¹³C and δD isotope analysis. The main objectives were focused on how different hydrological regimes in this ecosystem control organic matter …