Environmental Chemistry Commons^™

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) …

Synthesis Of N-Heterocyclic Molecules And Their Applicability Towards Ion Sensing: Polymeric Chemosensors, Aikohi M. Ugboya

College of Graduate Studies: Theses & Dissertations

Critical to biological and environmental processes are anions because often times their relative concentration in our body can be an indicator of one’s well-being. Therefore, highly sensitive and cost-efficient methods for ions recognition is necessary for human health. In recent times, polymeric chemosensors have become a vital tool for sensing ions because of its higher sensitivity and good mechanical properties compared to their monomeric counterparts. These sensors are designed to produce a measurable response in the presence of a targeted ion such as an electrochemical or optical signal. The unique structure and the photophysical properties of the 1,2,3-triazole core coupled …

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 …

Assessing Biofiltration Without Ozonation For Removal Of Trihalomethane Precursors In Drinking Water At The Beaver Water District Drinking Water Treatment Plant, Sana Ajaz

Graduate Theses and Dissertations

Biofiltration without pre-ozonation has the capability to remove natural organic matter (NOM) fractions that serve as precursors of disinfection byproducts (DBPs), which include the four regulated trihalomethanes (THMs) and dichloroacetonitrile (DCAN). Rapid small-scale column tests (RSSCTs) and Pilot Plant filters operated at empty-bed contact times (EBCTs) of 4, 8, and 16 minutes were used to evaluate the performance of nutrient-amended (free ammonia and phosphorus) biofiltration for THM and DCAN precursor removal, as measured using formation potential (FP) tests. NOM surrogates – which include dissolved organic carbon (DOC), specific ultraviolet absorbance (SUVA254) and fluorescence-PARAFAC components – were measured weekly throughout the …

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 …

Molecular Fossils From Phytoplankton Reveal Secular Pco2 Trend Over The Phanerozoic, Caitlyn R. Witkowski, Johan W. H. Weijers, Brian S. Blais, Stefan Schouten, Jaap S. Sinninghe Damsté

Science and Technology Department Faculty Journal Articles

Past changes in the atmospheric concentration of carbon dioxide (PCO2) have had a major impact on earth system dynamics; yet, reconstructing secular trends of past PCO2 remains a prevalent challenge in paleoclimate studies. The current long-term PCO2reconstructions rely largely on the compilation of many different proxies, often with discrepancies among proxies, particularly for periods older than 100 million years (Ma). Here, we reconstructed Phanerozoic PCO2 from a single proxy: the stable carbon isotopic fractionation associated with photosynthesis (Ɛp) that increases as PCO2 increases. This concept has been widely applied to alkenones, but here, we …

Consumption Profiles Of Illicit And Neuropsychiatric Drugs In Urban And Rural Communities In Kentucky Using Sewage Epidemiology, Tara Croft, Katelyn Foppe, Rhiannon Huffines, Bikram Subedi

Posters-at-the-Capitol

The drug overdose deaths in the USA increased by ~20% from 2015 to 2016 to the total >63,600 drug overdose deaths in 2016. Kentucky is among the highest rate of drug overdose death states in the USA. The current estimates of the prevalence of substance abuse are based on the self-reported surveys, overdose/toxicological reports, and drug-related crime statistics. Survey-based conventional approaches are not only cost and time-intensive but also underestimate the actual consumption of drugs. As “wastewater never lie,” the drug residues in raw wastewater collected from the centralized wastewater treatment plants were utilized to determine the consumption rate of …

Hot Spots And Hot Moments Of Soil Moisture Explain Fluctuations In Iron And Carbon Cycling In A Humid Tropical Forest Soil, Diego Barcellos, Christine S. O'Connell, Whendee L. Silver, Christof Meile, Aaron Thompson

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Soils from humid forests undergo spatial and temporal variations in moisture and oxygen (O₂) in response to rainfall, and induce changes in iron (Fe) and carbon (C) biogeochemistry. We hypothesized that high rainfall periods stimulate Fe and C cycling, with the greatest effects in areas of high soil moisture. To test this, we measured Fe and C cycling across three catenas at valley, slope, and ridge positions every two days for a two-month period in a rainforest in Puerto Rico. Over 12 days without rain, soil moisture, Fe^II, rapidly reducible Fe oxides (Fe^III_RR), …

From The River To The Gulf: An Investigation Of Biogeochemical Cycling In Wetland Soils And Coastal Shelf Sediments, Katie Bowes

LSU Master's Theses

Louisiana is home to 40% of the coastal wetlands in the lower 48 states, yet accounts for 80% of the coastal wetland loss in this region. This loss is attributed to decreased sediment supply, levee alteration, sea level rise, channelization, and subsidence. The levee system in Louisiana disconnected coastal wetlands from the main stem of the Mississippi River (MSR), reducing the amount of land-building sediment that reaches coastal wetlands. This disconnection also allows a greater percentage of river discharge, including agricultural contaminants and runoff, to flow into the northern Gulf of Mexico (NGOM).

The 2012 Coastal Master Plan proposed eight …

Eddy Flux Measurements Of Sulfur Dioxide Deposition To The Sea Surface, Jack G. Porter, Warren J. De Bruyn, Eric S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Deposition to the sea surface is a major atmospheric loss pathway for many important trace gases, such as sulfur dioxide (SO2). The air–sea transfer of SO2 is controlled entirely on the atmospheric side of the air–sea interface due to high effective solubility and other physical– chemical properties. There have been few direct field measurements of such fluxes due to the challenges associated with making fast-response measurements of highly soluble trace gases at very low ambient levels. In this study, we report direct eddy covariance air–sea flux measurements of SO2, sensible heat, water vapor, and momentum. The measurements were made over …

Influence Of Salinity, Sunlight, And Sediment On The Toxicity Of Pesticides In Three Non-Target Organisms, Emily Noelle Vebrosky

LSU Doctoral Dissertations

Pesticides used in the United States must undergo registration by the United States Environmental Protection Agency (USEPA), after a multitude of analyses ranging from environmental fate to aquatic toxicological impacts to human risk exposure. Testing varies for each chemical, some requiring more testing than others. In many cases, environmental factors are restricted in the analysis of chemical behavior and organismal testing is limited to larvae. Many pesticides are formulated to breakdown in the environment by means of photolysis, hydrolysis, or oxidation, either to ensure low-persistence, limited transport, or to form the active ingredient (pro-pesticides). Environmental influences on chemical behaviors include …

Photocatalytic Activity: Experimental Features To Report In Heterogeneous Photocatalysis, Md. Ariful Hoque, Marcelo I. Guzman

Chemistry Faculty Publications

Heterogeneous photocatalysis is a prominent area of research with major applications in solar energy conversion, air pollution mitigation, and removal of contaminants from water. A large number of scientific papers related to the photocatalysis field and its environmental applications are published in different journals specializing in materials and nanomaterials. However, many problems exist in the conception of papers by authors unfamiliar with standard characterization methods of photocatalysts as well as with the procedures needed to determine photocatalytic activities based on the determination of “apparent quantum efficiencies” within a wavelength interval or “apparent quantum yields” in the case of using monochromatic …

Data On Ion Composition And X-Ray Diffraction Patterns Of Biosolids From Wastewater Treatment Plants In Lufkin And Nacogdoches, Texas, Usa, Kefa Karimu Onchoke, Christopher M. Franclemont, Paul W. Weatherford

Faculty Publications

The data presented in this article is related to the research article entitled, “Structural Characterization and Evaluation of Municipal Wastewater Sludge (Biosolids) from two Rural Wastewater Treatment Plants in East Texas, USA”, Onchoke, KK, Franclemont, C.M., Spectrochim. Acta A, In press[1]. The XRD profiles and composition of biosolids from wastewater treatment plant is presented. This study describes the composition of XRD crystalline phase patterns of the wastewater sludge. After the removal of the Ka2 peaks the d-spacing and hkl values were determined. In addition, the ion chromatographic profile of the seven anions (NO₃^-, NO_{2 …}

Responses Of Daphnia Magna To Chronic Exposure Of Cadmium And Nickel Mixtures, Edgar Pérez, Tham C. Hoang

School of Environmental Sustainability: Faculty Publications and Other Works

The present study assessed the chronic toxicity of cadmium (Cd) and nickel (Ni) mixtures to Daphnia magna. Using a titration design, Ni concentrations of 20, 40, 80, 100, 120, 140, and 160 μg/L were tested alone and simultaneously titrated in increments against a constant concentration of 1.5 μg/L Cd. The results demonstrated that Cd at 1.5 μg/L was highly toxic to D. magna, and Ni alone concentrations ≥80 μg/L were toxic to D. magna survival, reproduction, and growth. No Ni alone concentration was found to induce a toxic effect on undeveloped embryos and the time to first brood. …

Short-Term Low Salinity Mitigates Effects Of Oil And Dispersant On Juvenile Eastern Oysters: A Laboratory Experiment With Implications For Oil Spill Response Activities, Meagan N. Schrandt, Sean Powers, F.Scott Rikard, Wilawan Thongda, Eric Peatman

University Faculty and Staff Publications

Following the Deepwater Horizon oil spill, eastern oyster (Crassostrea virginica) reefs in the northern Gulf of Mexico were exposed to oil and various associated clean-up activities that may have compromised oyster reef health. Included in the exposure was oil, dispersant, and in some locales, atypical salinity regimes. Oil and dispersants can be detrimental to oysters and the effects of salinity depend on the level. In addition to these extrinsic factors, genetic diversity of oyster populations may help the oysters respond to stressors, as demonstrated in other systems. We used a 3×3×2 factorial design to experimentally examine the effects …

An Overview Of Dynamic Heterogeneous Oxidations In The Troposphere, Elizabeth A. Pillar-Little, Marcelo I. Guzman

Chemistry Faculty Publications

Due to the adverse effect of atmospheric aerosols on public health and their ability to affect climate, extensive research has been undertaken in recent decades to understand their sources and sinks, as well as to study their physical and chemical properties. Atmospheric aerosols are important players in the Earth’s radiative budget, affecting incoming and outgoing solar radiation through absorption and scattering by direct and indirect means. While the cooling properties of pure inorganic aerosols are relatively well understood, the impact of organic aerosols on the radiative budget is unclear. Additionally, organic aerosols are transformed through chemical reactions during atmospheric transport. …

Deep Soils Modify Environmental Consequences Of Increased Nitrogen Fertilizer Use In Intensifying Amazon Agriculture, Kathijo Jankowski, Christopher Neill, Eric A. Davidson, Marcia Macedo, Ciniro Costa Jr., Gillian L. Galford, Leonardo Maracahipes Santos, Paul Lefebvre, Darlisson Nunes, Carlos E. P. Cerri, Richard Mchorney, Christine S. O'Connell, Michael T. Coe

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Agricultural intensification offers potential to grow more food while reducing the conversion of native ecosystems to croplands. However, intensification also risks environmental degradation through emissions of the greenhouse gas nitrous oxide (N₂O) and nitrate leaching to ground and surface waters. Intensively-managed croplands and nitrogen (N) fertilizer use are expanding rapidly in tropical regions. We quantified fertilizer responses of maize yield, N₂O emissions, and N leaching in an Amazon soybean-maize double-cropping system on deep, highly-weathered soils in Mato Grosso, Brazil. Application of N fertilizer above 80 kg N ha⁻¹ yr⁻¹ increased maize yield and N …

Enhanced Acidity Of Acetic And Pyruvic Acids On The Surface Of Water, Alexis J. Eugene, Elizabeth A. Pillar, Agustín J. Colussi, Marcelo I. Guzman

Chemistry Faculty Publications

Understanding the acid–base behavior of carboxylic acids on aqueous interfaces is a fundamental issue in nature. Surface processes involving carboxylic acids such as acetic and pyruvic acids play roles in (1) the transport of nutrients through cell membranes, (2) the cycling of metabolites relevant to the origin of life, and (3) the photooxidative processing of biogenic and anthropogenic emissions in aerosols and atmospheric waters. Here, we report that 50% of gaseous acetic acid and pyruvic acid molecules transfer a proton to the surface of water at pH 2.8 and 1.8 units lower than their respective acidity constants pK_{a …}

Cross Photoreaction Of Glyoxylic And Pyruvic Acids In Model Aqueous Aerosol, Sha-Sha Xia, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

Aerosols of variable composition, size, and shape are associated with public health concerns as well as with light-particle interactions that play a role in the energy balance of the atmosphere. Photochemical reactions of 2-oxocarboxylic acids in the aqueous phase are now known to contribute to the total secondary organic aerosol (SOA) budget. This work explores the cross reaction of glyoxylic acid (GA) and pyruvic acid (PA) in water, the two most abundant 2-oxocarboxylic acids in the atmosphere, under solar irradiation and dark thermal aging steps. During irradiation, PA and GA are excited and initiate proton-coupled electron transfer or hydrogen abstraction …

Investigation On The Dissociative Photoionization Mechanism Of Furfural, Investigation Of The Absolute Photoionization Cross Sections Of Three Potential Propargylic Fuels, And Ab Initio Analysis On Potential Superbases Of Several Hyperlithiated Species: Li3f2o And Li3f2(Oh)N (N = 1, 2, 3), Matthew Winfough

Master's Theses

This thesis presents the study photoionization cross sections of three different propargylic biofuels; dipropargyl ether, propargyl alcohol, and propargylamine, in chlorine radical-initiated combustion experiments at the Chemical Dynamics Beamline (9.0.2) at the Advanced Light Source of the Ernest Orlando Berkeley National Laboratory in Berkeley, California. Additionally, the unimolecular dissociative photoionization mechanism of furfural was studied using photoelectron photoionization coincidence (PEPICO) spectroscopy at the vacuum ultraviolet beamline at the Swiss Light Source of the Paul Scherrer Institut in Villigen, Switzerland. Dissociation products and mechanisms for furfural were identified over a photon energy range of 10.9 to 14.5 eV. Lastly, a study …

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 …

Geochemistry Of Archaeological And Marine Environments In Southwest Maine, Heather L. Bushie

Thinking Matters Symposium Archive

Two archaeological excavations for the University of Southern Maine collected sediment columns from select units for geological and chemical analysis. The Spiller Farms site is a Native American site located in Wells, Maine marking a transition period between the Pleistocene and Holocene epochs, 12,000 BP. The Malaga Island site was a historic mixed-race community at the north end of Casco Bay where sediment columns were obtained in near-shore and subtidal zones. The samples obtained from Malaga Island have been radiocarbon dated to 3800 +/- 30 BP at 23 meters below the low-tide line. X-ray fluorescence (XRF) analysis is being conducted …

Legacy Contaminants In The Northern Gulf Of Mexico Shelf, Jessica N. Landry

LSU Master's Theses

The Mississippi River watershed is the third largest in the world and drains from 31 states in the United States. Due to its route through the U.S., it passes through hundreds of EPA labeled Superfund sites as well as agricultural and suburban watersheds. These sites are known to have historical chemical contamination, and as a result chemicals can be transported by runoff down the Mississippi River into the Gulf of Mexico where their ultimate fate is unknown. Organochlorine chemicals are known to be persistent and are found in agricultural land as well as US EPA Superfund sites, especially DDT, PCBs, …

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 …

Presence And Potential Sources Of Pharmaceutical And Personal Care Product Chemicals In Messalonskee Lake, Alyssa T. Kullberg

Honors Theses

Pharmaceuticals and personal care product chemicals (PPCPs) represent a large group of contaminants that are mostly not regulated in surface or drinking water and whose presence and environmental and health impacts are poorly understood. We investigated the presence and potential sources of 18 PPCPs in Messalonskee Lake. We collected samples four times over the summer of 2017 at 13 sites around the lake. Samples were tested for PPCPs using liquid chromatography-tandem mass spectrometry. We detected five out of the 18 PPCPs we tested for at the ng/L level: caffeine, 1,7-dimethylxanthine, acetaminophen, sulfachloropyridazine, and amphetamine. PPCPs showed a significant positive correlation …

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 …

A Model To Predict Concentrations And Uncertainty For Mercury Species In Lakes, Ashley Hendricks

Dissertations, Master's Theses and Master's Reports

To increase understanding of mercury cycling, a seasonal mass balance model was developed to predict mercury concentrations in lakes and fish. Results indicate that seasonality in mercury cycling is significant and is important for a northern latitude lake. Models, when validated, have the potential to be used as an alternative to measurements; models are relatively inexpensive and are not as time intensive. Previously published mercury models have neglected to perform a thorough validation. Model validation allows for regulators to be able to make more informed, confident decisions when using models in water quality management. It is critical to quantify uncertainty; …

Development Of Photocatalysts Supported On Graphitic Carbon Nitride For The Degradation Of Organic Water Pollutants, Atanu Giri

Theses and Dissertations

Graphitic carbon nitride (g-C₃N₄) heterojunction composites with the semiconducting metal oxides, CeO₂, ZnO and TiO₂ are prepared in situ by co-calcination of the precursor materials or by a solvothermal method. The structural, morphological and the optical properties of the prepared materials are studied using various microscopy and spectroscopy techniques. The synthesized composite materials, CeO₂/g-C₃N₄, ZnO/g-C₃N₄ and TiO₂/g-C₃N₄ are more efficient in the photocatalytic degradation of the water pollutants indigo carmine (IC) and atrazine than the pure metal oxide, g-C …

Significance Of A Non-Thermal Plasma Treatment On Ldpe Biodegradation With Pseudomonas Aeruginosa, Laurence Scally, Miroslav Gulan, Lars Weigang, Vladimir Milosavljević, Patrick J. Cullen

Articles

The use of plastics has spanned across almost all aspects of day to day life. Although their uses are invaluable, they contribute to the generation of a lot of waste products that end up in the environment and end up polluting natural habitats such as forests and the ocean. By treating low-density polyethylene (LDPE) samples with non-thermal plasma in ambient air and with an addition of ≈4% CO2, the biodegradation of the samples can be increased due to an increase in oxidative species causing better cell adhesion and acceptance on the polymer sample surface. It was, however, found that the …

Testing The Underlying Chemical Principles Of The Biotic Ligand Model (Blm) To Marine Copper Systems: Measuring Copper Speciation Using Fluorescence Quenching, Tara N. Tait, James C. Mcgeer, Scott Smith

Chemistry Faculty Publications

Speciation of copper in marine systems strongly influences the ability of copper to cause toxicity. Natural organic matter (NOM) contains many binding sites which provides a protective effect on copper toxicity. The purpose of this study was to characterize copper binding with NOM using fluorescence quenching techniques. Fluorescence quenching of NOM with copper was performed on nine sea water samples. The resulting stability con- stants and binding capacities were consistent with literature values of marine NOM, show- ing strong binding with log K values from 7.64 to 10.2 and binding capacities ranging from 15 to 3110 nmole mg C ^{−1 …}