Chemistry Commons^™

Spectroscopic Characterization Of Dissolved Organic Matter: Insights Into Composition, Photochemical Transformation And Carbon Cycling, John Robert Helms

Chemistry & Biochemistry Theses & Dissertations

This dissertation explores processes affecting the composition of dissolved organic matter (DOM) and how DOM composition changes in sunlit surface waters and in the dark interior ocean. Simulated solar irradiations were used to investigate the impact of photochemistry on terrestrial waters and deep ocean DOM. The photochemically mediated processes observed in Dismal Swamp samples included (i) light induced flocculation of up to 12% of the organic matter and 84% of the dissolved iron originally present; (ii) 74-88% mineralization of dissolved organic carbon (DOC) and 95-99% bleaching of chromophoric DOM (CDOM) during 110 days of irradiation; and (iii) nearly complete loss …

Global Estimates Of Mineral Dust Aerosol Iron And Aluminum Solubility That Account For Particle Size Using Diffusion-Controlled And Surface-Area-Controlled Approximations, Qin Han, Charles S. Zender, J. Keith Moore, Clifton S. Buck, Ying Chen, Anne Johansen, Christopher I. Measures

All Faculty Scholarship for the College of the Sciences

Mineral aerosol deposition is recognized as the dominant source of iron to the open ocean and the solubility of iron in the dust aerosol is highly variable, with measurements ranging from 0.01–80%. Global models have difficulty capturing the observed variations in solubility, and have ignored the solubility dependence on aerosol size. We introduce two idealized physical models to estimate the size dependence of mineral aerosol solubility: a diffusion‐controlled model and a surface‐area‐controlled model. These models produce differing time‐ and space‐varying solubility maps for aerosol Fe and Al given the dust age at deposition, size‐resolved dust entrainment fields, and the aerosol …

Strawberry Growth, Yield, Fruit Nutrition, And Control Of Verticillium Wilt With Pre-Plant Soil Fumigants, Ozone, And Biological Control, Justin J. Scurich

Master's Theses

Verticillium wilt is a widespread soilborne disease of strawberry historically controlled by soil fumigation with methyl bromide (MB). MB was banned by the United Nations in 1995 and will be completely phased out by 2015. Research has concentrated on alternative methods of disease control without finding a single alternative able to replace MB in widespread disease control and yield increase. For the current study, strawberries were greenhouse grown in container pots filled with soil from both infested and non-infested areas of a commercial strawberry field in Watsonville, CA. Treatments included pre-plant soil fumigation with commercially available formulations of methyl bromide, …

Modeling Regional Radicarbon Trends: A Case Study From The East Texas Woodland Period, Robert Z. Selden Jr.

CRHR: Archaeology

The East Texas Radiocarbon Database contributes to an analysis of tempo and place for Woodland era (~500 BC–AD 800) archaeological sites within the region. The temporal and spatial distributions of calibrated ¹⁴C ages (n = 127) with a standard deviation (ΔT) of 61 from archaeological sites with Woodland components (n = 51) are useful in exploring the development and geographical continuity of the peoples in east Texas, and lead to a refinement of our current chronological understanding of the period. While analysis of summed probability distributions (SPDs) produces less than significant findings due to sample size, they are used …

Ua94/6/10 Student / Alumni Personal Papers Wku Carl Ellis, Wku Archives

WKU Archives Collection Inventories

Scientific notebooks used by Carl Ellis during his years at WKU.

Observation Of Sulfate Aerosols And So₂ From The Sarychev Volcanic Eruption Using Data From The Atmospheric Chemistry Experiment (Ace), D. Doeringer, A. Eldering, C. D. Boone, G. González Abad, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

[1] Infrared spectra measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) on the SCISAT satellite were used to analyze the Sarychev volcanic aerosol after the eruption in June 2009. Evidence of the Sarychev eruptions was first detected in July 2009 from enhanced SO₂ concentrations and atmospheric extinction. By February 2010, the atmosphere had returned to pre-Sarychev conditions. In July 2009, the volcanic plume was found between 8.5 km and 17.5 km in altitude at mid- and high latitudes (55°N–70°N). The first SO₂ and sulfate aerosol retrievals carried out using the infrared solar occultation spectra recorded with …

Process-Evaluation Of Tropospheric Humidity Simulated By General Circulation Models Using Water Vapor Isotopologues: 1. Comparison Between Models And Observations, Camille Risi, David Noone, John Worden, Christian Frankenberg, Gabriele Stiller, Michael Kiefer, Bernd Funke, Kaley Walker, Peter Bernath, Matthias Schneider, Debra Wunch, Vanessa Sherlock, Nicholas Deutscher, David Griffith, Paul O. Wennberg, Kimberly Strong, Dan Smale, Emmanuel Mahieu, Sabine Barthlott, Frank Hase, Omaira García, Justus Notholt, Thorsten Warneke, Geoffrey Toon, David Sayres, Sandrine Bony, Jeonghoon Lee, Derek Brown, Ryu Uemura, Christophe Sturm

Chemistry & Biochemistry Faculty Publications

The goal of this study is to determine how H₂O and HDO measurements in water vapor can be used to detect and diagnose biases in the representation of processes controlling tropospheric humidity in atmospheric general circulation models (GCMs). We analyze a large number of isotopic data sets (four satellite, sixteen ground-based remote-sensing, five surface in situ and three aircraft data sets) that are sensitive to different altitudes throughout the free troposphere. Despite significant differences between data sets, we identify some observed HDO/H₂O characteristics that are robust across data sets and that can be used to evaluate …

Atmospheric Effects Of Energetic Particle Precipitation In The Arctic Winter 1978-1979 Revisted, L. A. Holt, C. E. Randall, V. L. Harvey, E. E. Remsberg, G. P. Stiller, B. Funke, P. F. Bernath, K. A. Walker

Chemistry & Biochemistry Faculty Publications

[1] The Limb Infrared Monitor of the Stratosphere (LIMS) measured polar stratospheric enhancements of NO₂ mixing ratios due to energetic particle precipitation (EPP) in the Arctic winter of 1978–1979. Recently reprocessed LIMS data are compared to more recent measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) and the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) to place the LIMS measurements in the context of current observations. The amount of NO_x (NO + NO₂) entering the stratosphere that has been created by EPP in the mesosphere and lower thermosphere (EPP-NO_x) has been quantified …

Process-Evaluation Of Tropospheric Humidity Simulated By General Circulation Models Using Water Vapor Isotopic Observations: 2. Using Isotopic Diagnostics To Understand The Mid And Upper Tropospheric Moist Bias In The Tropics And Subtropics, Camille Risi, David Noone, John Worden, Christian Frankenberg, Gabriele Stiller, Michael Kiefer, Bernd Funke, Kaley Walker, Peter Bernath, Matthias Schneider, Sandrine Bony, Jeonghoon Lee, Derek Brown, Christophe Sturm

Chemistry & Biochemistry Faculty Publications

Evaluating the representation of processes controlling tropical and subtropical tropospheric relative humidity (RH) in atmospheric general circulation models (GCMs) is crucial to assess the credibility of predicted climate changes. GCMs have long exhibited a moist bias in the tropical and subtropical mid and upper troposphere, which could be due to the mis-representation of cloud processes or of the large-scale circulation, or to excessive diffusion during water vapor transport. The goal of this study is to use observations of the water vapor isotopic ratio to understand the cause of this bias. We compare the three-dimensional distribution of the water vapor isotopic …

Atr-Ftir Studies On The Kinetics Of Dimethylarsinic Acid (Dma) Surface Complexation With Iron(Oxyhydr)Oxides, Julia Tofan-Lazar Miss

Theses and Dissertations (Comprehensive)

Dimethylarsinic acid (DMA) is an organoarsenical compound that, along with monomethylarsonic acid, poses a health and an environmental risk, and a challenge to the energy industry. Little is known about the surface chemistry of DMA at the molecular level with materials relevant to geochemical environments and industrial sectors. The surface chemistry of phosphorus and arsenic compounds in their organic and inorganic forms is of great interest due to its role in controlling their transport, bioaccessibility and speciation. This thesis reports the first in-situ and surface-sensitive rapid kinetic studies on the adsorption and desorption of DMA to and from Fe-(oxyhydr)oxide films …

Petrography And Geochemistry Of Mafic Granulites Of The Ubendian Belt: Contribution To Insights Into The Lower Continental Crust Of The Paleoproterozoic, N. Boniface

Tanzania Journal of Science

Mafic granulites of the Ubendian Belt have geochemical signature, trace and REE patterns, similar to that of the lower continental crustal rocks. A SHRIMP U-Pb single zircon date at 1977±40 Ma indicates that these rocks belong to the Paleoproterozoic Ubendian orogenic cycle, which was followed by the Mesoproterozoic tectonic disturbance that contributed to their exhumation. Orthopyroxene, clinopyroxene, garnet, hornblende, plagioclase and quartz is a frequent mineral assemblage for the mafic granulites of the Ubendian Belt, and garnet frequently form corona between plagioclase and clinopyroxene. Geothermobarometric calculations have revealed the equilibration of these rocks at a temperature range between 650 and …

Spatial And Temporal Variations In The Air-Sea Carbon Dioxide Fluxes Of Florida Bay, Christopher Michael Dufore

USF Tampa Graduate Theses and Dissertations

The flux of CO2 between the ocean and the atmosphere is an important measure in determining local, global, and regional, as well as short term and long term carbon budgets. In this study, air-sea CO2 fluxes measured using a floating chamber were used to examine the spatial and temporal variability of CO2 fluxes in Florida Bay. Measurements of dissolved inorganic carbon and total alkalinity obtained concurrently with chamber measurements of CO2 flux allowed calculation of ΔpCO2 from flux measurements obtained at zero wind velocity. Floating chamber measurements of ΔpCO2 were subsequently coupled with wind speed data to provide a simple …

Effects Of Weathering On Aromatic Compounds In Beach Tars From The Deepwater Horizon Disaster, Gulf Of Mexico Coast, Usa, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Operators aboard the Deepwater Horizon drilling platform lost control of the Macondo No. 1 well about 90 km southwest of the Louisiana coast on April 20, 2010, leading to a catastrophic release of ca. 550 Gg of crude oil over the next 86 days [1]. Oil from the spill soon found its way to nearby coastal areas, leaving tarry deposits on beaches and marshes. Oil was reported on the beach at Gulf Shores, Alabama (180 km northeast of the well) on June 5 and the relatively fresh sample discussed herein (GSA) was collected that same day. Oil reached the beach …

Eerc Laboratory Capabilities, University Of North Dakota. Energy And Environmental Research Center

EERC Brochures and Fact Sheets

Brochure about the Energy & Environmental Research Center (EERC) laboratory facilities, equipment, and capabilities. Includes information on Analytical Research Laboratory, Natural Materials Analytical Research Laboratory, Applied Geology Laboratory, and Environmental Chemistry Laboratory. [This item is an outdated or superseded version and retained for historical purposes only. It may no longer reflect current information, policies, or practices.]

The Vinylguaiacol/Indole Or Vgi ("Veggie") Ratio: Assessing Relative Contributions Of Terrestrial And Aquatic Organic Matter To Sediments, Michael A. Kruge, Kevin K. Olsen, Jaroslaw W. Slusarczyk, Elaine Gomez

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

In studies of the organic matter (OM) fraction of marine, estuarine, fluvial, or lacustrine sediments, one of the most fundamental distinctions to be made is that between terrestrial and aquatic OM. To supplement the parameters commonly used for this purpose (e.g., C/N and stable isotope ratios), we proposed the Vinylguaiacol/Indole or VGI ("Veggie") ratio, defined as [vinylguaiacol / (indole + vinylguaiacol)] using data produced by analytical pyrolysis-gas chromatography/mass spectrometry of dried, homogenized sediment samples [1]. The ratio employs the peak areas of these two compounds on the mass chromatograms of their molecular ions (m/z 150 and 117, respectively). Major pyrolysis …

Exploring Methods For Earthquake Prediction: The Effects Of Water On The Flow Of Stress-Activated Electric Currents In Igneous Rocks, Aaron M. Jahoda, Friedemann T. Freund

STAR Program Research Presentations

Much of the devastation and damage of earthquakes can be attributed to the fact that they occur suddenly and without much warning, which limits the ability of people to evacuate and/or properly prepare. One method, however, that might be used to predict seismic events is the generation of electric currents in rocks when stresses are applied. It is observed in this research that the application of direct force onto samples of igneous rock causes the rocks to generate a measurable current, which is attributed to positive-hole charges moving within the oxygen sub-lattice. Because large and changing forces are acted upon …

The Nature, Origin And Preservation Of Amide Organic Nitrogen In Organic Matter, Georgina Anne Mckee

Chemistry & Biochemistry Theses & Dissertations

Past studies have found much of nonliving sedimentary/aqueous nitrogen-containing organic matter (NCOM) is composed of amides, assumed to be peptides/proteins. Their lability calls into question their survival, and several hypotheses have been suggested to explain this. Using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and nuclear magnetic resonance (NMR) spectroscopy I investigated the molecular amide composition in sedimentary/aqueous systems while reassessing their preservation and formation routes.

Development of a suitable methodology is essential for successful NCOM study due to electrospray ionisation source requirements: sediment samples need to be rendered into solution. Based on NMR and FT-ICR-MS analysis, I determined …

Insights Into Chemical Structure Changes Of Kerogen From Bituminous Coal In Response To Dike Intrusions Investigated By Advanced Solid-State 13C Nmr, Yuan Li

Chemistry & Biochemistry Theses & Dissertations

Variations in the chemical structures of kerogens From highly volatile bituminous coal located near two igneous dike intrusions in the Illinois Basin were examined in detail by advanced solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Spectral-editing techniques were used to identify specific functional groups. Direct polarization was used to quantify different functional groups. ¹H-¹³C two- dimensional heteronuclear NMR was used to examine connectivities and proximities, and ¹H-¹³C long-range recoupled dipolar dephasing was used to estimate aromatic cluster sizes. With decreasing distance to dike contacts and increasing thermal maturity (vitrinite reflectance R₀ from …

Determining The Lon-Exchange Mechanism Of Strontium Into A Niobium Doped Titanosilicate, Samantha Jane Kramer

Masters Theses & Specialist Projects

A 25% niobium substituted sitinakite was exchanged with strontium as time resolved X-ray diffraction data was collected. The structural modeling of this data by Rietveld method1 has lead to the determination of the atomic positions of the ions and unit cell parameters as strontium occupancy increases.

The starting material of the exchange experiment is the protonated phase, H2Nb0.67Ti1.33SiO7·1.9 H2O, with space group P42/mcm2,3. Once strontium (Sr2+) enters the unit cell, extra-framework H2O molecules shift to provide the necessary hydration coordination. These new positions of H2O result in a lowering of symmetry to the P-42m space group, and it is thought …

Approach To Arsenic And Selenium Removal From Fly Ash By Oxalate And Estimation Of Calcium Effects On Both Elements, Ying Wen

Masters Theses & Specialist Projects

An approach to arsenic and selenium removal from fly ash is studied. This research includes a comparison of the leaching ability of ammonium oxalate, ammonium citrate, ammonium nitrate and EDTA to extract arsenic and selenium; use of common agricultural waste as a source of oxalate anion to remove arsenic and selenium from fly ash and estimation of additional calcium effects on arsenic and selenium leaching behaviors.
This research shows that extraction strength order is EDTA > ammonium oxalate > ammonium citrate > ammonium nitrate > water, achieving arsenic extraction efficiencies of 94.18%, 84.17%, 4.50%, 2.89% and 0.18%, respectively; achieving selenium extraction efficiencies of 96.14%, …

Determination Of Caffeine As A Marker For Septic Tank Contamination Of Wilgreen Lake, Rosemary Onjiko, Susan Godbey, Walter S. Borowski, Darrin Smith, Lori Wilson

EKU Faculty and Staff Scholarship

Wilgreen Lake in Richmond, Kentucky, has been listed by both the state and the Environmental Protection Agency as an “impaired” lake due to excess nutrients, which may be in part contributed by domestic septic systems. Caffeine can be used as an anthropogenic marker to estimate the contribution of septic tank effluent to the lake. We have modified existing analytical methods to produce a viable method for the determination of caffeine in environmental water samples and applied the method to water samples collected from Wilgreen Lake. The modified method allows determination of caffeine in a concentration range of 75 to 10,000 …

Evaluation Of The Sensitivity Of Inventory And Monitoring National Parks To Nutrient Enrichment Effects From Atmospheric Nitrogen Deposition Northern Great Plains Network (Ngpn), T. J. Sullivan, T. C. Mcdonnell, G. T. Mcpherson, S. D. Mackey, D. Moore

United States National Park Service: Publications

Northern Great Plains Network (NGPN)

National maps of atmospheric N emissions and deposition are provided in Maps A and B as context for subsequent network data presentations. Map A shows county level emissions of total N for the year 2002. Map B shows total N deposition, again for the year 2002.

There are three parks in the Northern Great Plains Network that are larger than 100 square miles: Badlands (BADL), Missouri (MNRR), and Theodore Roosevelt (THRO). In addition, there are 10 other smaller parks.

Total annual N emissions, by county, are shown in Map C for lands in and surrounding …

Variations In Concentrations And Compositions Of Polycyclic Aromatic Hydrocarbons (Pahs) In Coals Related To The Coal Rank And Origin, Susanne Laumann, Vesna Micic Batka, Michael A. Kruge, Christine Achten, Reinhard Sachsenhofer, Jan Schwarzbauer, Thilo Hofmann

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The release of unburnt coal particles and associated polycyclic aromatic hydrocarbons (PAHs) may cause adverse impacts on the environment. This study assessed variations in the concentration and composition of PAHs in a set of fifty coal samples from eleven coal basins worldwide. The maximum PAH concentrations at high volatile bituminous rank were recorded in samples from a single basin. Considering the entire sample, the highest PAH concentrations were in fact found outside of this rank range, suggesting that the maceral composition and thus the coal's origin also influenced PAH concentrations. The examination of the PAH compositions revealed that alkylated 2-3 …

Fossil And Contemporary Aerosol Particulate Organic Carbon In The Eastern United States: Implications For Deposition And Inputs To Watersheds, Andrew S. Wozniak, James E. Bauer, Rebecca M. Dickhut

Chemistry & Biochemistry Faculty Publications

Atmospheric particulate matter samples were collected from mid-Atlantic and northeastern U. S. (Virginia and New York, respectively) sites to assess the fossil versus contemporary sources contributing to aerosol organic carbon (OC) and the implications for its deposition to watersheds. Mean particulate matter total OC (TOC) deposition rates (wet + dry deposition) were calculated to be 1.6 and 2.4 mg C m^-2 d^-1 for the Virginia and New York sites, respectively. Wet deposition of particulate TOC was determined to be the dominant depositional mode, accounting for >65% (Virginia) and >80% (New York) of total aerosol TOC deposition. Isotopic mass …

The Vinylguaiacol/Indole Or Vgi ("Veggie") Ratio: A Novel Molecular Parameter To Evaluate The Relative Contributions Of Terrestrial And Aquatic Organic Matter To Sediments., Michael A. Kruge, Kevin K. Olsen, Jaroslaw W. Slusarczyk, Elaine Gomez

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The organic matter (OM) fraction of estuarine sediments is often distinctive and thus diagnostically useful in determinations of sedimentary provenance. Among the most fundamental distinctions to be made is that between terrestrial and aquatic OM. To supplement the parameters commonly used for this purpose (e.g., C/N and stable isotope ratios), we proposed the Vinylguaiacol/Indole or VGI ("Veggie") ratio, defined as [vinylguaiacol / (indole + vinylguaiacol)] using data produced by analytical pyrolysis-gas chromatography/mass spectrometry of dried, homogenized sediment samples. The ratio employs the peak areas of these two compounds on the mass chromatograms of their molecular ions (m/z 150 and 117). …

Hrc Enews — 2010 Fall, Megan K. Svarz

Publications (HRC)

This issue contains staff accomplishments and announcements, event listings, and a "new faces" listing for new staff, affiliates, and researchers.

2,2′,5,5′-Tetra­Chloro­Benzidine, Onome Ugono, Marcel Douglas, Nigam Rath, Alicia Beatty

Chemistry & Biochemistry Faculty Works

In the crystal structure of the title compound, C12H8Cl4N2, mol­ecules lie on crystallographic twofold axes at the centre of the C-C bonds linking the benzene rings, such that the asymmetric unit consists of a half-mol­ecule. The individual mol­ecules participate in inter­molecular N-H...N, N-H...Cl, C-H...Cl and Cl...Cl [3.4503 (3) Å] inter­actions.

A Novel Pervious Cement Reaction Barrier (Pcrb) In Situ Arsenic Remediation System, Morgan Liane Jones

Masters Theses & Specialist Projects

No abstract provided.

Adaptivearc And The Future Of The Energy Industry, Trevor Chase

Earth and Soil Sciences

No abstract provided.

Relatin Dissolved Oxygen Concentration To Fish Distribution In Jarecki Lake, Adam Sutton

Department of Environmental Studies: Undergraduate Student Theses

Abstract Water temperature and dissolved oxygen (DO) profiles were measured once every month from mid July to mid February in a relatively deep sand-pit lake in southeast Nebraska. These profiles showed depleted DO concentrations below the thermocline during summer stratification indicating areas fish will likely avoid in summer months. Colder temperatures in fall caused complete mixing of the water column allowing fish to inhabit all depths of the lake. An inverse temperature stratification occurred directly below the ice during winter months as ice cover cooled the surface water to below 4 degrees Celsius. Ice cover also blocked air – water …